Diamondoids

Pan Stanford Series on Renewable Energy — Volume 2

Diamondoids
Synthesis, Properties, and
Applications

editors
Preben Maegaard
Anna Krenz Sven Stauss
Wolfgang Palz Kazuo Terashima

The Rise of Modern Wind Energy

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Diamondoids: Synthesis, Properties, and Applications

Copyright 
c 2017 Pan Stanford Publishing Pte. Ltd.

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ISBN 978-981-4745-18-5 (Hardcover)

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 Contents

Symbols and Abbreviations xi

Preface xiii

PART I DIAMONDOIDS: STRUCTURES, PROPERTIES,

AND APPLICATIONS

1 Introduction 3

2 Structure, Nomenclature, and Symmetry of Diamondoids 9

2.1 Diamondoids and Their Relation to Other Carbon
Nanomaterials 9
2.2 The Structure of Diamondoids 12
2.3 Classification of Diamondoids 14
2.4 Nomenclature and Classification of Diamondoids 18
2.4.1 The von Baeyer Naming Scheme 19
2.4.2 Nomenclature of Diamondoids Based on
Dualist Graphs 22
2.4.3 Regular and Irregular Polymantanes 30
2.4.4 Formula Partition Periodic Table 31
2.5 Molecular Symmetry and Crystal Structures of
Diamondoids 34
2.5.1 Molecular Symmetry of Diamondoids 35
2.5.2 Crystal Structures of Diamondoids 35
2.6 Differences between Diamondoids and
Nanodiamonds 38
vi Contents

3 Chemical and Physical Properties and Characterization of

Diamondoids 41
3.1 Chemical Properties 41
3.1.1 Thermodynamic Properties 44
3.1.2 Chemical Stability 45
3.1.3 Solubility of Diamondoids in Gases, Organic
Solvents, and Supercritical Fluids 50
3.1.3.1 Solubility in organic solvents 50
3.1.3.2 Solubility in gases and supercritical
fluids 53
3.1.4 Biocompatibility and Toxicity 55
3.2 Physical Properties 57
3.2.1 Electronic Properties 57
3.2.1.1 The band structure of diamondoids 58
3.2.1.2 Effect of diamondoid size on bandgap 60
3.2.1.3 HOMO-LUMO variation by
functionalization of diamondoids 63
3.2.1.4 Variation of the HOMO-LUMO gap by
the inclusion of small atoms inside
diamondoids 64
3.3 Optical Properties 68
3.3.1 Vibrational Spectroscopy of Diamondoids 68
3.3.1.1 Infrared spectroscopy 68
3.3.1.2 Raman spectroscopy of diamondoids 68
3.4 Mass Spectrometry of Diamondoids 77
3.4.1 Nuclear Magnetic Resonance Spectroscopy of
Diamondoids 77

4 Current and Future Applications of Diamondoids and

Their Derivatives 81
4.1 Overview 81
4.2 Applications of Diamondoids in Oil Exploration 82
4.2.1 Formation of Diamondoids in Natural Gas
Reservoirs 83
4.3 Current and Possible Future Applications of
Diamondoids and Derivatives in Chemistry,
Pharmaceutics, Medicine, and Biotechnology 86
 Contents vii

4.3.1 Applications in Chemistry 86

4.3.1.1 Host–guest chemistry 86
4.3.2 Applications of Diamondoids in Pharmaceutics
and Medicine 86
4.3.3 Current and Possible Future Applications of
Diamondoids for Drug Delivery 92
4.4 Applications in Materials Science and Nanotechnology 94
4.4.1 Materials Science 94
4.4.2 Diamondoids as an Electron Source 96
4.5 Possible Future Applications of Diamondoids 100
4.5.1 Biotechnology 101
4.5.2 Quantum Computing and Communication 101
4.5.3 Magnetometry 102
4.5.4 Nanorobots and Molecular Machines 103
4.6 Summary 105

PART II ISOLATION AND ORGANIC CHEMICAL

SYNTHESIS OF DIAMONDOIDS
5 Occurrence and Isolation of Diamondoids from Natural
Gas and Oil Reservoirs 109
5.1 Occurrence of Diamondoids in Natural Gas and
Oil Reservoirs 109
5.2 Formation of Diamondoids in Natural Sources 111
5.3 Isolation of Diamondoids from Gas and Oil 115
5.3.1 Alternative Purification Methods 116

6 Approaches for the Organic Synthesis of Diamondoids 119

6.1 A Brief History of the Isolation and Organic
Synthesis of Diamondoids 120
6.2 Conventional Organic Chemical Synthesis of
Diamondoids 121
6.2.1 Synthesis of Adamantane 121
6.2.2 Synthesis of Diamantane 122
6.2.3 Synthesis of Triamantane 126
6.2.4 Synthesis of Tetramantane 128
6.3 Limitations of the Organic Synthesis of Diamondoids 129
viii Contents

PART III NOVEL APPROACHES FOR THE SYNTHESIS OF

DIAMONDOIDS BY MICROPLASMAS
7 Diamondoid Synthesis by Electric Discharge Microplasmas
in Supercritical Fluids 133
7.1 Introduction 133
7.2 Generation of Plasmas in Supercritical Fluids 136
7.3 Electric Discharges in High-Pressure and
Supercritical Fluid Microreactors 140
7.3.1 Investigation of Possible Diamondoid
Reaction Paths by GC-MS Analysis of
Intermediate Products 151

8 Synthesis of Diamondoids by Pulsed Laser Plasmas 157

8.1 Application of Pulsed Laser Plasmas in
Supercritical Fluids to Nanomaterial Synthesis 161
8.2 Synthesis of Diamondoids by Pulsed Laser
Plasmas 162
8.3 Micro-Raman Spectroscopy 163
8.4 Gas Chromatography–Mass Spectrometry 166
8.4.1 Synthesis of Diamantane 166
8.4.2 Possible Synthesis of Diamondoids
with n ≥ 3 167
8.4.3 Effects of Pyrolysis on Synthesized
Products 172
8.5 Comparison between PLA in scCO2 and scXe 173
8.6 Conclusions and Perspectives 174

9 Synthesis of Diamondoids by Atmospheric-Pressure

Microplasmas 177
9.1 Introduction 177
9.2 Microchip Microplasma Reactors 179
9.3 Plasma Generation and Characterization 181
9.3.1 Optical Emission Spectroscopy
Measurements 183
9.3.2 GC-MS Analysis of Diamantane and
Reaction Intermediates 185
9.4 Summary 189
 Symbols ix

10 Conclusions and Perspectives 191

Appendix 193
A.1 Character Code Tables of Diamondoids 193
Bibliography 195
Index 221
 Symbols and Abbreviations

List of Symbols
Cp Heat capacity
E Energy
Eb Binding energy (eV)
E VBM Valence band maximum
FD Density fluctuation
Mr Relative molecular weight
p Pressure (Pa)
pcrit Critical pressure (Pa)
T Temperature (K)
Tcrit Critical temperature (K)
V Volume (m3 )
Vappl Applied voltage (kV)
Vp-p Peak-to-peak voltage (kV)
β Compressibility
κ Heat conductivity

List of Abbreviations
CP Critical point
B3LYP Becke, three-parameter Lee–Yang–Parr exchange
correlation functional used for DFT
DFT Density functional theory
DOS Density of electronic states
GC-MS Gas chromatography–mass spectrometry
xii Symbols and Abbreviations

HOMO Highest occupied molecular orbital

LUMO Lowest unoccupied molecular orbital
SIM Selected ion monitoring
SXE Soft X-ray emission
 Preface

Like a modern drama, one could consider this book to consist of

three main acts: In the first act, we set the stage for the topic and
expose the main actors, that is, diamondoids, and their relation to
other carbon nanomaterials. In the same part, we delve more deeply
into the chemical and physical properties of diamondoids and give
an overview of their current and possible future applications.
In the second part of the book, we, little by little, approach the
main complications related to the application of especially larger
diamondoids: the current approaches for obtaining diamondoids
and the current attempts to obtain them by conventional chemical
synthesis. In particular, we aim at demonstrating the different
problems associated with the various conventional approaches.
Finally, in the third part, we present possible alternative
solutions for synthesizing diamondoids from the smallest mem-
ber, adamantane, using plasmas generated in supercritical fluids.
Because the field of plasmas generated in such high-density fluids is
still not known to a wide audience, we are first briefly presenting the
properties and applications of supercritical fluids before discussing
the properties of electric discharge and pulsed laser plasmas
generated in supercritical fluids.
The last part of the book deals with the application of such
plasmas for diamondoids in more detail before giving a final
assessment of the current state of the research on diamondoids.
Molecular diamonds, commonly called diamondoids, are a very
interesting class of carbon nanomaterials that can be considered
the archetypical molecular building block. While still not as widely
known as other carbon nanomaterials, such as carbon nanotubes
and graphene, previous and current research shows that this class of
xiv Preface

materials holds a lot of promise for many different fields of science

and nanotechnology.
One of the goals in preparing this book was to introduce
interested readers to the field of diamondoids; their structure,
chemical, and physical properties; and the different isolation and
synthesis approaches that currently exist. In addition to conven-
tional isolation and synthesis approaches, we also introduce new
ones, especially those based on electric discharge and pulsed laser
plasmas generated inside supercritical fluids and at atmospheric
pressure.
We hope that the present book will be useful not only as both
an introductory and a reference text on diamondoids but also as
an inspiration for further research on this remarkable class of
nanomaterials.
This book is mainly aimed at researchers and graduate students
who are curious about the field of diamondoids, that is, materials
science, physics, and chemistry, but we hope that it will also be
interesting for persons from other fields of science and technology.
One of our goals in writing this book was to make it an intro-
ductory text on diamondoids aimed at researchers and graduate
students active in the field and at the same time to make it also a
stand-alone text so that people who are not familiar with certain
topics do not have to refer to the scientific literature themselves.
Special care was given to the figures and graphs. Whenever
possible, we remade both graphs and figures in this book in order
to avoid raster images as much as possible. In the cases where we
have relied on data from other publications, we have indicated all the
original data sources and references. We also tried to make the figure
and table captions as self-explanatory as possible so that people who
just want to flip through the book can understand the main points of
an illustration or graph without having to resort to the main text.
For those readers who wish to delve more deeply into the field
of diamondoids, we have compiled a comprehensive list of the
current scientific literature. Especially the field of organic synthesis
of diamondoids is very vast. However, for the convenience of the
readers, we have limited ourselves to those references that can
currently be accessed electronically.
 Preface xv

In writing this book, we have tried to remain as general and make

the contents as enduring as possible, but at the same time we also
wanted to provide the reader with the latest results of the research
on diamondoids. However, we are fully aware that with todays rapid
pace with which science and technology advance, the contents of this
book might become outdated quite rapidly. Nevertheless, we hope
that this will not happen too soon and that it can serve researchers
from many different backgrounds as a reference and hopefully also
as an inspiration for their own research.
A very special thank-you goes to Stanford Chong for suggesting
this book project and his patience and encouragement during the
writing process. We are also indebted to all the staff at Pan Stanford
Publishing for their efforts in bringing this book to print.
We would like to thank the following persons for their support in
the work related to this book:
• Prof. Takehiko Sasaki for his help with mass spectrometry
measurements and comments concerning the interpreta-
tion of the results
• Prof. Hiroshi Kataoka and Dr. Minoru Suzuki (now at Shi-
madzu Corp.) for their support with gas chromatography–
mass spectrometry measurements and helpful discussions
• Prof. Tohru Suemoto and Prof. Motoyoshi Baba (now at
Saitama University) for their help with pulsed laser ablation
• Dr. Keiichiro Urabe (now at Air Liquide) for commenting on
one of the very early drafts of the manuscript
• All present and former students of the Terashima Lab for
the work presented in this text
Concerning the experiments on diamondoid synthesis, we would
like to thank Dr. Takaaki Tomai (now at Tohoku University), Dr.
Hiroyuki Miyazoe (now at IBM Thomas J. Watson Research Center),
Hirokazu Kikuchi, Sho Nakahara, Tomoki Shizuno, Fumita Oshima,
Chikako Ishii, Satoshi Kato, and Koichi Kuribara. We would also like
to thank Dr. David Z. Pai (Université de Poitiers) for his contribution
to atmospheric-pressure diamondoid synthesis.
Since the topic of diamondoids encompasses various branches of
science and readers are most probably from many different fields
of science, we have tried to keep the text as self-explanatory as
xvi Preface

possible. Especially organic chemists might find our treatment of

organic synthesis too basic; however, as some of the readers (and
the authors) do not have a background in organic chemistry, we hope
that they can bear with us.
As any book, probably this one also contains many errors
and oversights, and any mistakes in the text are entirely the
responsibility of the authors. We are grateful for any feedback from
the readers, and we are grateful for any feedback from the readers
to point us to these.
Finally, we hope that the book can serve both as a reference text
and an inspiration, both for seasoned researchers and new students,
and that the field of diamondoids can grow more in the future.
This work was supported financially in part by a Grant-in-
Aid for Scientific Research on Innovative Areas (Frontier Science
of Interactions between Plasmas and Nano-interfaces, Grant No.
21110002) from the Ministry of Education, Culture, Sports, Science,
and Technology of Japan. The authors thank the Materials Design
and Characterization Laboratory, Institute for Solid State Physics,
University of Tokyo, for providing access to the pulsed laser facility.

Sven Stauss
Kazuo Terashima
Kashiwa and Tokyo, Japan
 PART I

DIAMONDOIDS: STRUCTURES,
PROPERTIES, AND APPLICATIONS
Chapter 1

Introduction

With the turn of the 21st century, the fabrication and synthesis
of new materials have become paramount either for further
enhancing existing or for enabling new applications. For example,
the combination of new process technologies and the use of new
semiconductor materials has allowed decreasing the characteristic
size of functional components in electronic circuits and memories
and to realize “more than Moore.”
Since the demonstration of the first working transistor at
Bell Laboratories by John Bardeen, Walter Brattain, and William
Shockley in 1947, the number of transistors that can be packed
on a chip has doubled roughly every 18 months. The relationship
between this duration and the doubling of the number of transistors
on a chip has become known as Moore’s law (Moore, 1998). The
evolution of the number of transistors as a function of time and in
comparison to Moore’s law is depicted in Fig. 1.1.
Up to now, with the advancement and optimization of new
processing technologies, the characteristic sizes of transistors
are approaching the order of a few nanometers. Currently, the
characteristic dimensions of electronic components are reaching
orders of a few nanometers, and while recent new applications
and nonplanar transistor designs, for example, fin-shaped field-

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
4 Introduction

Microprocessor Transistor Counts & Moore’s Law

16-Core SPARC T3
Six-Core Core i7
Six-Core Xenon 7400
2’600’000’000 Dual-Core Itanium 2
10-Core Xeon WestmereEX
8-core POWER7
AMD K10 Quad-Core z196
1’000’000’000 POWER6
Quad-Core Itanium Tukwila
8-Core Xeon Nehalem-EX
Itanium 2 with 9MB cache Six-Core Opteron 2400
AMD K10 Core i7 (Quad)
Core 2 Duo
Itanium 2 Cell

100’000’000 AMD K8

Pentium 4 Barton Atom

Number of transistors

AMD K7
AMD K6 AMD K6-III
10’000’000 Pentium III
Pentium II
AMD K5
Pentium

80486
1’000’000

80386

80286
100’000
68000
80186
8086 8088

8085
10’000 6800 6809
8080 Z80
8008 MOS 6502
2’300 4004
RCA 1802

1971 1980 1990 2000 2011

Date of introduction

Figure 1.1 Evolution of the number of transistors. The graph displays the
variation from 1970 to 2011, together with microprocessor families. The
solid line corresponds to the count of transistors doubling every two years.
Data adapted from Moore (1998).

effect transistors (finFETs), allow overcoming certain limitations of

conventional two-dimensional silicon-based transistors, ultimately,
the current approach will reach its physical limit that cannot be
overcome and further shrinking of transistors will not be possible
anymore.
The advancement and decrease of the feature sizes are driven by
not only the optimization of the processing steps, a decrease of the
wavelength in the light sources used for lithography, etc., but also
the integration and combination of new materials. In contrast to
conventional top-down approaches, where functional components
are fabricated using macroscopic masks, etc., bottom-up processing
has been suggested as an alternative. In this approach, functionality
is achieved by using molecular building blocks consisting of
nanoparticles, nanowires, etc.
 Introduction 5

Similar behavior has been observed also for other electronic

components, for example, hard disks, where the capacity has been
shown to double in a similar fashion, or the resolution of displays,
where pixel densities are also increasing to the extent that individual
pixels cannot be distinguished anymore by the naked eye.
The trend of this exponential increase in the number of
transistors or other electronic components has been driven by
improvements of processing, for example, the decrease of the
characteristic feature sizes using light sources of smaller and smaller
wavelengths.
Currently, characteristic dimension of electronic components
reaching orders of a few nanometers, and while recent new appli-
cations, for example, finFETs, allow to overcome certain limitations
of conventional transistors, ultimately, the current approach will hit
a dead end.
Because of this, in recent years, other types of processing
techniques, so-called bottom-up, have gained increasingly interest
as an alternative to conventional top-down fabrication methods. Top-
down techniques heavily rely on repetitive of patterning, deposition,
and etching, the feature size being determined by the wavelength
of the light source used during patterning, as well as characteristics
of, for example, the plasma chemistry. In bottom-up techniques,
larger building blocks are obtained by guided self-assembly of atoms,
clusters, or wires (cf. Fig. 1.2.)
Currently, predictions of the shrinking of characteristic feature
sizes in microchips have become less aggressive, concomitant with
a reduction in the pace of new technologies. The main difficulty in
further reducing gate widths is the limits imposed by conventional
microfabrication processes. The physical limit of downsizing of gate
widths is expected to be reached at 5 nm, because leakage currents
become too high (Iwai, 2009).
On the other hand, it has been proposed that novel materials, for
example, novel III–V compound semiconductors, could permit one
to solve some of the problems encountered by conventional silicon-
based devices (del Alamo, 2011).
Nanomaterials are gaining increasing interest and are finding
more and more their way from scientific laboratories to industrial
applications. Among these are Si nanowires, which have shown
6 Introduction

Top down
Inkjet printing Capillary
assembly

Patterning Photo- Nanoimprint

lithography lithography

Micro- and
Nano fabrication
Host-guest Covalent
chemistry immobilization

Assembling
Electrostatic Self-assembly
layer-by-layer
deposition

Bottom up

Figure 1.2 Illustration of conventional top-down and bottom-up processes.

Figure adapted from Curri et al. (2010).

promise as material transistors, for sensors but also for enhancing

the efficiency of photovoltaic cells. Because Si can store about 10
times more Li when compared to graphite, it also has shown promise
for use in Li ion batteries.
Another very important field of research that has become more
and more important is biotechnology. To develop new pharmaceu-
ticals and also to understand molecular processes occurring inside
cells, organs, and bodies of organisms, new methods have to be
devised. For observing molecular processes inside cells, different
types of nanomarkers are used, such as fluorescent nanoparticles.
Such nanomarkers typically consist of nanoparticles that have been
functionalized by attaching a fluorescent molecule to them or that
already contain color centers that are fluorescent (e.g., diamonds
that contain nitrogen vacancy defects). One constraint that such
nanoparticles have to fulfill is that they are biocompatible and
that they are nontoxic. Conventionally, functionalized inert metallic
nanoparticles such as gold have been used as fluorescent particles.
In addition to metallic nanoparticles, semiconductor nanoparti-
cles are gaining more and more attention due to the many different
possibilities that are offered by their doping.
 Introduction 7

Besides these types of nanomaterials, those based on carbon are

one of the most important. Carbon is one of the most abundant
elements on earth, and owing to the possibility of different
hybridization, many different nanomaterials can be obtained, such
as fullerenes, carbon nanotubes, graphene, and nanodiamonds (the
relation between these different classes will be discussed in detail
in Chapter 2. In addition to these, in recent years nanodiamonds,
with sizes in the range of ∼5–20 nm have been used increasingly,
owing to their nontoxicity and biocompatibility. In addition, the
presence of carbon allows functionalization with relative ease. The
main topic of this book is a special class of carbon nanomaterials,
diamond molecules, also called diamondoid hydrocarbons or simply
diamondoids.
In contrast to other types of nanomaterials, for example, metallic
nanoparticles but also nanodiamonds, their structure and sizes are
well defined, and they possess a very high thermal and structural
stability.
The topic of this book is a special class of carbon nanomaterials,
diamond molecules, synonymously called diamondoid hydrocar-
bons, polymantanes, or simply diamondoids. Diamondoids are
aliphatic cage structures, that is, they consist of a carbon framework
saturated completely by hydrogen terminations.
Because of their well-defined structure, they represent the
archetypical molecular building block, and as we will show in
subsequent parts of this book, this is one reason why they show
promise for a wide range of applications where they could probably
replace currently used nanomaterials.
The contents of this book are structured as follows: In
Chapter 2, we introduce diamond molecules—diamondoids—
and discuss their relation to other carbon nanomaterials
(carbon nanotubes, graphenes, etc.). We also give a brief
introduction to the nomenclature of diamondoids and briefly
discuss the molecular symmetries of diamondoids and the crys-
talline structure of solid diamondoids. Chapter 3 properties of
diamondoids.
In Chapter 4, we present current and possible future applications
of diamondoids in various scientific and technological fields,
medicine, pharmaceutics, and opto- and nanoelectronics. We also
8 Introduction

present a few topics where possibly one day diamondoids could

replace currently used macroscale diamonds or nanodiamonds,
namely in quantum computing and quantum communication.
In the second part of this book, that is, Chapters 5 and 6, we
present the current approaches to isolating diamondoids from oil
and gas reservoirs and the approaches to obtaining them by organic
chemical synthesis.
In the final part of the Chapter 7 to 9, we present alternative
approaches for the synthesis of diamondoids, which are based
on plasmas generated in supercritical fluids and at atmospheric
pressure.
We conclude the book with a brief summary of and an outlook
on possible future directions in the field of diamondoids, their
synthesis, and their applications.
Chapter 2

Structure, Nomenclature, and Symmetry

of Diamondoids

In this chapter, we first introduce the different structures of carbon

nanomaterials that arise as a result of their hybridization. A part of
this chapter is also devoted to the classification and nomenclature
of diamondoids, and the crystal structures of diamondoids. Finally,
we also make a brief comparison between diamondoids and nano-
diamonds, and point out their principal analogies and differences.
As will be explained in more detail in this chapter, compared to the
macroscale counterparts, that is, diamond, in nanodiamonds and
diamondoids, both the size and surface chemistry impart electronic
and magnetic properties (Enoki et al., 2009). A more general
treatise on carbon nanomaterials and nanotechnology can be found
in (Krueger, 2010).

2.1 Diamondoids and Their Relation to Other

Carbon Nanomaterials
Estimates place carbon as the fourth-most abundant element in the
sun and solar system (Atkins et al., 2010), and carbon at the

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
10 Structure, Nomenclature, and Symmetry of Diamondoids

macroscopic scale can exist under different forms or allotropes:

amorphous carbon, graphite, cubic diamond, and hexagonal dia-
mond (Lonsdaleite).
In the last 50 years, other members of carbon allotropes
at the nanoscale have been discovered: linear carbon chains
such as carbyne/polyyne, fullerenes, carbon nanotubes, graphene,
nanodiamonds and diamondoids. The reason for the ability of
carbon to form different chemical bonds that result in different
allotropes is related to the electronic structure of carbon. In carbon,
with the atomic number 6, the occupation of the different orbitals
in the ground state is 1s2 2s2 2p1x 2p1y . The 2s and 2p valence orbitals
of carbon can be combined to form different hybridized orbitals,
leading to the formation of sp1 , sp2 , and sp3 orbitals. Figure 2.1

a b x x x
Carbon 2p

2s y z +y z y z

2s 2pz sp hybrids
1s x x x

z + z z
y y y

c y y y
2p2 hybrids
x+ x+ x

2s 2px 2py

d z z z z 2p3 hybrids

y+ y+ y+ y

2s 2px 2py 2pz

Figure 2.1 Electronic configuration and hybridization of carbon. (a)

Occupation of core and valence shells in carbon. The linear combination
of the 2s and 2p orbitals leads to the formation of different orbitals.
(b) Combination of one 2s and one 2p orbital: Formation of sp1 orbital.
(c) Formation of sp2 orbital by the combination of one 2s and two 2p
orbitals. (d) Combination of one 2s and 2px , 2p y , and 2pz orbitals leads to the
formation of sp3 , whose principal axes point to the edges of a tetrahedron.
 Diamondoids and Their Relation to Other Carbon Nanomaterials 11

illustrates the electron occupation of the orbitals of C atoms and the

formation of sp1 -, sp2 -, or sp3 -hybridized orbitals. In the case of the
sp3 orbitals, the lobes point to the edges of a tetrahedron and are
separated by an angle of 109.5◦ .
The classification of carbon materials based on the dimensional-
ity of their structure, and their basic properties, has been discussed
in an extensive review (Shenderova et al., 2002). Figure 2.2
illustrates the different carbon nanostructures that result from

Carbyne (sp1) Graphite (sp2)

...=C=C=C=C=...
Cumulene

Graphene

Butadiene

Ovalene
sp1 + 2π sp2 + π
Polyyne C Carbon
nanotubes

sp 3

Corannulene
Molecular
scale
C60
Adamantane
Fullerenes
(C70, C84, ...)
Nanoscale Diamondoids
(d < 2 nm)

Macroscale

Nanodiamond

Diamond (sp3)

Figure 2.2 Overview of carbon nanostructures formed as a consequence

of the different hybridizations of C, sp1 , sp2 , and sp3 . For sp3 -hybridized
carbon nanostructures, corannulene can be considered as a building block
for fullerene and carbon nanotubes, whereas ovalene can be considered
as a graphene precursor. In contrast to fullerenes, carbon nanotubes, and
graphene, the C−C bonds in diamondoids (defined to have characteristic
sizes d < 2 nm) are sp3 hybridized and the building block can be considered
to be adamantane. Figure adapted from Shenderova et al. (2002).
12 Structure, Nomenclature, and Symmetry of Diamondoids

the different hybridizations of carbon. As shown in the figure,

C(sp1 )−C(sp1 ) bonds lead to linear structures such as cumulenes
and polyynes. The former consist of at least three consecutive
C double bonds, whereas in the latter, the linear chain is formed by
alternating single and triple C bonds.
For C(sp2 )−C(sp2 ) bonds, a large variety of planar or curved
structures can be formed—fullerenes, carbon nanotubes (CNTs), or
graphene.
In contrast to these well-known carbon nanomaterials, especially
fullerenes, CNTs and graphene, the structure of macroscopic
diamond, nanodiamonds, and molecular diamond—also called
diamondoid hydrocarbons or simply diamondoids—consists of
C(sp3 )−C(sp3 )-hybridized bonds. The structure of diamondoids are
formed by carbon cages that can be superimposed on a diamond
lattice. As will be explained in more detail in the following sections,
in contrast to nanodiamonds, the terminations of the carbon
cage structure are well-defined and usually consist of hydrogen
atoms.

2.2 The Structure of Diamondoids

The first diamondoid member is called adamantane, after the
Greek word for diamond (αδ άμαζ —adámas, “unconquerable,”
“indestructible”). Adamantane has the chemical formula C10 H16 and
consists of a single cage that can be formed by fusing cyclohexanes
in chair formation. All the C atoms in the structure of adamantane
are C(sp3 )−C(sp3 )-hybridized, the dangling bonds being terminated
by H atoms.
The relation between the structure of adamantane and the
diamond lattice is illustrated in Fig. 2.3a, where the carbon
framework of one adamantane is superimposed on the one of the
diamond. As can be seen in Fig. 2.3b, which displays adamantane as
both stick and van der Waals sphere models, it is highly symmetric,
its point group being Td (the symmetry elements belonging to this
group and the implications for the interpretation of vibrational
spectra will be discussed in Sections 2.5 and 3.3.1). As we will
see in a following chapter, this high symmetry results in physical
 The Structure of Diamondoids 13

a Diamond lattice b H C
Unit cell
of diamond

[010]
[001]
[100]
Adamantane

z
z z y x
x y x y

Figure 2.3 Relation of cubic diamond lattice and adamantane. (a) The
unit cell and a 577-carbon-atom lattice of cubic diamond along the main
crystallographic directions [100], [110], and [111] and its relation to the
molecular structure of the smallest diamondoid, adamantane, whose carbon
framework is indicated in red. (b) Adamantane, displayed in both stick
and van der Waals sphere representations, consists of 10 carbon and 16
hydrogen atoms and is the basic unit of diamondoid hydrocarbons. (c)
Adamantane in relation to diamond unit cell along three different viewing
directions [100], [110], and [111]. For clarity, the hydrogen atoms are not
displayed.

properties that set adamantane apart from hydrocarbons of similar

molecular mass. Finally, the unit cell of the diamond accommodates
adamantane, whose apical atoms occupy the centers of faces of the
diamond unit cell (cf. Fig. 2.3c).
As will be explained in the next section, the distinction between
diamondoids and nondiamondoids is made based on whether a
molecule consists of at least one complete adamantane unit. We
will discuss in more detail the difference between diamondoids and
nondiamondoids and then explain the classification of diamondoids
14 Structure, Nomenclature, and Symmetry of Diamondoids

consisting of face-fused adamantanes, so-called polymantanes,

which are the main topic of this book.

2.3 Classification of Diamondoids

In the discussion of the classification of diamondoids, we follow
the treatment that has been presented in the seminal paper on
diamondoids by Balaban and von Schleyer (Balaban and Schleyer,
1978).
Diamondoids or diamond hydrocarbons are generally defined as
“molecules whose arrangement of C atoms allows total or partial
superposition on the diamond lattice.” However, this is true for many
hydrocarbons that are not typically associated with diamondoids.
Molecules whose structures can be superimposed on the diamond
lattice include, for example, cyclohexane, decalin, simple alkanes
(including methane), and also structures close to the diamond lattice
such as cyclodecane, and bicyclo[3.3.1]nonane, but since they do not
include at least one complete adamantane unit, they are considered
as nondiamondoids.
In contrast, structures like the adamantane dimer belong to
the class of diamondoids. Diamondoids are therefore defined as
“hydrocarbons possessing at least one adamantane unit which are
totally or largely superimposable on the diamond lattice” (Balaban
and Schleyer, 1978). The distinction between diamondoid and
nondiamondoid hydrocarbons and a few representative examples is
illustrated in Fig. 2.4. For the sake of clarity, in the representations
of these structures, the hydrogen terminations are not displayed.
As shown in the figure, only molecules that consist of at least
one complete adamantane unit, are classified as diamondoid
hydrocarbons.
Next, we will examine more in detail the different types of
molecular structure that are assigned to diamondoid hydrocarbons.
The flowchart in Fig. 2.5 illustrates the separation into different
subgroups, depending on whether the adamantane containing
molecular structures are only partially or completely superimpos-
able on the diamond lattice, and how many elements between
adamantane units—atoms, edges, and faces—are shared.
 Classification of Diamondoids 15

Diamondoids Nondiamondoids

Cyclohexane
H H
Adamantane
H

H
trans-Decalin cis-Decalin

Adamantane dimer

Bicylco[3.3.1]nonane Cyclodecane

Figure 2.4 Distinction between diamondoid and nondiamondoid hydrocar-

bons. Diamondoids are hydrocarbons consisting of at least one complete
adamantane unit. In contrast, structures that can also be superimposed
on the diamond lattice but that do not contain one complete adamantane
unit do not belong to the class of diamondoids. After Balaban and Schleyer
(1978).

Molecules that contain at least one adamantane unit can be

classified into the two main groups I and II:
I: those that are partially superimposable
II: those that are completely superimposable
on the diamond lattice. For molecules belonging to group II, they are
further classified into two subgroups, depending on whether
(1) Not all atoms of the molecule belong to adamantane units
(2) All atoms are members of an adamantane unit
Members of group (2) can be further divided into those that consist
of either
16 Structure, Nomenclature, and Symmetry of Diamondoids

Totally
superimposable I NO
on diamond
lattice

II YES

All C atoms
belong to complete (1) NO
adamantane
units

(2) YES
(a)

Adamantane units NO
non-isolated

YES
(b) Spiro-fused

Common C atom
More
than 5 C atoms
NO
common to 2 or more (c) Edge-fused
adamantane
units
2 Common edge
(d) Composite-fused
YES

(e) Face-fused (Polymantanes) 3 4 5

6 (1) 9 (2) 12 (3) 13 (3)

Figure 2.5 Flowchart illustrating the classification of diamondoid hydro-

carbons or diamondoids. The classification here follows the exposition
in Balaban and Schleyer (1978). The two main groups are those that are
only partially superimposable on the diamond lattice (group I) and those
that possess molecular structures that can be completely superimposed
(group II). With increasing number of shared C atoms and edges, one finally
obtains structures where adamantane units share faces, and these types
of structures are named polymantanes. In the case of groups (b–d), the
numbers indicate the C atoms shared, whereas in (e), the numbers indicate
the shared C atoms and the number of shared faces (in parentheses).
 Classification of Diamondoids 17

(a) Nonisolated adamantane units

and those that are either fused by

(b) One common C atom (spiro fused)

(c) Two common C atoms (fused by one edge of the adaman-
tane cage)
(d) Either 3, 4 or 5 common C atoms (2, 3 or 4 shared edges)

Finally, the last group is

(e) Two adamantane have 6 common C atoms, that is, sharing

one face of the adamantane unit

These face-fused structures are called polymantanes and they are

the class of diamondoid hydrocarbons that are the main topic of this
text. The molecular structures of groups (b–e) displayed in Fig. 2.5
illustrate the increasing number of shared C atoms and edges of the
adamantane cage (the numbers below the molecules indicating the
number of shared C atoms and number of shared edges).
Following the smallest of the polymantanes, adamantane (cage
number n = 1), the next larger member is diamantane that consists
of two face-fused adamantane units (n = 2). As will be explained in
more detail, the commonly accepted nomenclature of polymantanes
uses Greek numerals as prefixes, followed by -mantane, that
indicate the number of fused adamantane units. By face-fusing
three adamantanes, one obtaines triamantane (n = 3). Starting
with tetramantane (n = 4), structural isomers can be formed
and the possibilities of arranging the diamondoid cages increases.
Consequently, diamondoids with n < 4 are also called lower
diamondoids, whereas for n ≥ 4, they are called higher diamondoids.
The details of the nomenclature and detailed classification of
diamondoids will be discussed below.
Looking at the structures in Fig. 2.6, it becomes evident that
for an increasing number of cages n, that the possibilities of the
arrangement of adamantane units also increases. In this figure,
the lines and vertices inside the structures of the diamondoids,
represent the dualist graphs, which will be treated in detail in
Section 2.4.2.
18 Structure, Nomenclature, and Symmetry of Diamondoids

1 Adamantane

Diamantane
2 Lower diamondoids

3
Triamantane

Higher diamondoids
Tetramantanes
4

Pentamantanes

number
of cages
n
n-mantane

Figure 2.6 Molecular structures of lower and higher diamondoids and

their relation to the diamond lattice. Structures of the lower diamondoids
adamantane, diamantane, triamantane and their relation to an idealized
577-carbon diamond lattice (it is supposed that the diamond is terminated
by hydrogen atoms, which are not shown for the sake of clarity). For
the diamondoids from n = 1 to n = 5 the dualist graphs used in
the systematic classification of diamondoids (Balaban and Schleyer, 1978)
are also indicated as lines connecting the vertices at the center of the
adamantane unit. Diamondoids with n < 4 are named lower diamondoids,
whereas for n ≥ 4, they are called higher diamondoids.

2.4 Nomenclature and Classification of

Diamondoids
In this section, we briefly introduce the two main naming
conventions that have been adopted for diamondoids. The first
part focuses on the systematic IUPAC naming scheme introduced
by von Baeyer (Baeyer, 1900) for polycyclic compounds, while
the second part introduces the naming scheme of polymantanes
 Nomenclature and Classification of Diamondoids 19

commonly used for diamondoids that was devised by Balaban and

von Schleyer (Balaban and Schleyer, 1978), and which is based on
dualist graphs.

2.4.1 The von Baeyer Naming Scheme

For illustrating the von Baeyer naming scheme, we briefly demon-
strate its application for the first two diamondoid members,
adamantane and diamantane. The official IUPAC name consists of
three parts: a prefix, which indicates the number of closed rings in
the molecule, a middle part that lists the lengths of carbon chains
or bridges connected to the main ring, and finally a suffix which
indicates the total number of carbon atoms.
Therefore, the procedure for assigning the name can be broken
down into three distinct steps, (1), (2), and (3). In the first step, the
number of closed cycles the molecule is made of has to be deduced.
As shown in Fig. 2.7, adamantane consists of three closed cycles,
with atom sequences 1 −2 −3 −10 −7 −8 , 3 −4 −5 −6 −7 −10 ,
and 1 −8 −7 −6 −5 −9 (cf. Fig. 2.7). Alternatively, the number of
cycles can also be determined from the total number of faces and
subtracting one, or the number of scissions that are necessary to
make the molecule linear (Filik, 2010). For example, adamantane
has four faces, and three scissions are necessary to make it linear.
The Greek number of cycles then gives the prefix of the name, that is,
tricyclo- in the case of adamantane.
The next step consists in determining the longest closed ring of
the C framework in the molecule. For adamantane, the longest closed
ring consists of 8 atoms (cf. step (2) for adamantane in Fig. 2.7).
Then, the two main bridgeheads, which are those C atoms that
are linked to three or four other carbons in the diamondoid, have
to be determined. Because of its symmetry, adamantane has four
bridgeheads at positions 1, 3, 5, and 7. From all possible choices,
the two main bridgeheads are selected in a fashion that allows to
obtain the longest bridges or chains of C atoms. Consequently, in the
case of adamantane, the two main bridgeheads are at positions 1
and 5. Then the bridges and the number of carbon atoms in all the
bridges joining the two main bridgeheads are counted. There are 3
bridges connecting the two main bridgeheads, two containing three
20 Structure, Nomenclature, and Symmetry of Diamondoids

Adamantane
(1) 7
(2) 7 Main ring (3) 7 2
6 6
1 3
8 8
10 1
Main
9 1 1 1
5 5 bridgehead
32
4 3 4 3 1 3
2 2

tricyclo [ 3. 3. 1. 13,7 ] decane

Diamantane
(1) (2) (3)
10
11
12 14
10
11
12 1 11 2 12 3 1
5
6
5
4
3 4 5
6 1 4 6
9 13 9 1 1 4
3 3
8 7
2
8 7
2 1 72
27 6

pentacyclo [ 7. 3. 1. 14,12. 02,7. 06,11 ] tetradecane

Figure 2.7 Example of the von Baeyer nomenclature of adamantane and

diamantane. The procedure for finding the name consists basically of three
steps: (1) Determine the number of closed cycles the molecule is made of;
the Greek digit of the number of cycles is the prefix, for example, tricyclo-
for three; (2) find the longest closed cycle of the molecule; assign the main
bridgeheads (C atoms that are connected to at last three other C atoms); and
(3) list the number of C atoms in the different bridges connected to the main
bridgeheads. For C atoms that are not connected to the main bridgeheads,
indicate the C atoms’ positions that are at the start and end of the bridge
as superscripts. Finally the last component of the name is the Latin digit of
total C atoms in the molecule (e.g., -decane for adamantane and -tetradecane
for diamantane).

atoms, and one bridge with one. There is one more bridge containing
1 C atom between positions 3 and 7, which is not connected to the
main bridgeheads. In this case, the positions of the C atoms are
added as superscripts and separated by commas to the number of
C atoms. The numbers of bridge atoms are then placed in square
brackets, separated by points: [3.3.1.13, 7 ]. Finally, the Latin term for
the total number of C atoms in the molecule is added as a suffix,
 Nomenclature and Classification of Diamondoids 21

that is, -decane for adamantane. Combining these three elements, the
IUPAC name of adamantane is tricyclo[3.3.1.13, 7 ]decane.
In the case of diamantane, the procedure is identical, except that
identifying the largest closed cycle and the two main bridgeheads
becomes more complicated, as illustrated in Fig. 2.7. As the
molecular structure of diamantane contains five closed rings, its
prefix is pentacyclo-. The longest cycle in the structure consists of
12 C atoms, and there are 8 bridgeheads (at positions 1, 2, 4, 6, 7,
9, 11, and 12). The two main bridgeheads are assigned to C atoms 1
and 9, and there are three bridges that are connected to them, one
containing 7 C atoms (sequence 2 −3 −4 −5 −6 −7 ), one with three
(10 −11 −12 ), and one with a single C atom (connecting C atoms 1
and 9). Then there is one bridge with one C atom linking atoms 4 and
12, and two bridges containing no C atom but linking C atoms 2 two
7 and 6 to 11. Finally, the von Baeyer designation of diamantane is
pentacyclo[7.3.1.14, 12 .02, 7 .06, 11 ]tetradecane.
The example of diamantane shows that for more complex
diamondoid structures, the procedure becomes too involved to
determine the corresponding von Baeyer name. There are a few
methods that can simplify the procedure outlined above. One is
based on using planar graphs, that is, the projection of the 3D
molecular structure of a diamondoid along a given direction onto
a plane (so-called Schlegel diagrams). This aids in determining
the number of closed rings, the main ring in the structure, and
the bridgeheads (Eckroth, 1967). As an example, Fig. 2.8 shows the
structures and corresponding Schlegel diagrams for the first three
diamondoids, adamantane, diamantane, and triamantane.
However, even these methods become too laborious for
larger diamondoids. For example, the next diamondoid after dia-
mantane, triamantane, is heptacyclo[7.7.1.13, 15 .01, 12 .02, 7 .04, 13 .06, 11 ]
octadecane. Consequently, for the naming of more complex diamon-
doids, computer algorithms are used (Balaban and Rucker, 2013),
which has permitted to also correctly determine IUPAC names of
functionalized diamondoids.
22 Structure, Nomenclature, and Symmetry of Diamondoids

7 2
10 1 14
6 3
8
8 7 9
3 4 5 4 13
12
1 10
2 9
Adamantane 5 6
11
Diamantane

4
3
3
2 10 4 5 2 13
7 14 1
6
7 8
8 9
1 5
10
6 12
9
11

13 11 5
14 12 6
5 10 3 13
7 11
4 1 6
15 17 9 8 9 10
16
18 3 7 2
2 8 17
18 12 14
Triamantane 1
16
15

Figure 2.8 Molecular structures and corresponding Schlegel diagrams of

adamantane, diamantane, and triamantane. Projecting the 3D structure
along one axis on a plane allows one to identify the closed cycles, the longest
ring and the main bridgeheads in the diamondoid structure more easily.
After Eckroth (1967).

2.4.2 Nomenclature of Diamondoids Based on Dualist

Graphs
While very flexible, for diamondoids, the von Baeyer scheme
results in very unwieldy names, for example,
4, 12 2, 7 6, 11
pentacyclo[7.3.1.1 .0 .0 ]tetradecane for diamantane, and
heptacyclo[7.7.1.13, 15 .01, 12 .02, 7 .04, 13 .06, 11 ]octadecane for triaman-
tane (Balaban, 2012). For this reason and to avoid the proliferation
 Nomenclature and Classification of Diamondoids 23

of trivial names that could have otherwise been introduced as

alternatives to the von Baeyer naming scheme, Balaban and
von Schleyer (Balaban and Schleyer, 1978) proposed an elegant
and simple nomenclature based on dualist graphs. From the dualist
graph codes, the structure of the diamondoids can be deduced much
more easily.a
A dualist graph of a diamondoid can be likened to a linear,
branched, or closed alkane, that itself can again be superimposed on
the diamond lattice. In other words, a dualist graph of diamondoids
is self-dualist. To generate a dualist graph, one starts from the
center of an adamantane cage. One then connects this first vertex
to the center of the next adjacent adamantane unit, following one
of possible four directions (1, 2, 3, or 4), pointing to the edges of a
tetrahedron (cf. Fig. 2.9). Adamantane has four faces, and because
only these four directions are possible when connecting an adjacent
adamantane unit, it is not necessary to indicate positive or negative
directions, the direction becoming obvious from the position of the
adamantane unit.
The procedure of connecting the vertices of the different
adamantane units is then repeated until the whole diamondoid can
be traced, adding the digits corresponding to the different directions
to the dualist code. In the case of branched diamondoids, one
chooses the permutation of the dualist code that represents the
longest chain connecting the adamantane units of the diamondoid.
The number of chains linking the adamantane cages are placed
in brackets, for example, [12] for triamantane, that is, the number of
elements in the dualist code of an n-mantane consist of n − 1 digits.
When the diamondoid contains branches, the direction vectors
pointing to these units from the main chain are placed into
parentheses, for example, [1(2)3]tetramantane. When at a given
vertex, two branches are present, they are placed in parentheses
and separated by a comma, for example, [1(2, 3)4]pentamantane.
In the case of longer branches, the chains of the branch are placed

a While dual graphs are frequently used in applied mathematics to describe the
connectivity of closed surfaces, dualist graphs are different from dual graphs, since
in dualist graphs, the distances and angles are fixed.
24 Structure, Nomenclature, and Symmetry of Diamondoids

inside parentheses, without separating them by a comma, such as in

[12(12)34]heptamantane.
Since there are always several permutations possible, a few
conventions have been adopted. One is that the chosen sequence
of direction vectors of the dualist graph are starting from the
lowest indices. In addition, if the diamondoid contains branches, the
elements in parentheses indicating these branches are moved as far
to the end of the sequence as possible.
Figure 2.9 shows the structures and the construction of the dual-
ist graphs for the lower diamondoids adamantane, diamantane, and
triamantane, and all of the possible structures and corresponding
dualist graphs of the first higher diamondoid, tetramantane.
Finally, [121(2)34]- and [12(12)34]heptamantane illustrate the
convention of dualist graphs if a branch consists of more than one
adamantane unit.
The list below summarizes additional rules for constructing
a dualist graph of diamondoids (Balaban and Schleyer, 1978).
Specifically, the following combinations are not allowed:
• . . . 111 . . .: Repeating digits
• . . . 1(1 . . .: Repeating digits
• . . . 1(2)1 . . .: Repeating digits before and after parentheses
• . . . 1(2, 3)1 . . .: Repeating digits before and after parentheses
• . . . 1(2, 3)2 . . .: Repeating two inside and after parentheses;
only 4 is allowed in this instance
• . . . 1): The last digit inside a parenthesis cannot be 1
• 124 . . .: Lowest number rule (the last digit should be 3)
• 1214 . . .: Lowest number rule (the last digit should be 3)
As has been shown in the previous section, diamondoids can
conceptually be formed by fusing together the basic adamantane
units. Because the lower diamondoids (adamantane, diamantane,
and triamantane) do not possess any structural isomers, only one
permutation of the dualist graph is possible and consequently, the
dualist codes of these three diamondoids are usually not written.
From tetramantane (n = 4), the cages can be fused together by
three different possibilities. As shown in Fig. 2.6, with increasing
cage number n, the possibilities of cage arrangements increase.
Furthermore, from diamondoids with n ≥ 6, it is possible to
 Nomenclature and Classification of Diamondoids 25

2
2

1
1 4 1

3
[1] [12]

3 4
1
2 2
2 2 3
1 1 1 1

[121] [123] [1(2)3]

2 4
1 3 2
4 1
3
2
1 2
1

[121(2)34] [12(12)34]

Figure 2.9 Construction of dualist graphs for polymantanes. The vertices of

the dualist graph are the centers of the adamantane cages. A dualist graph
of a diamondoid is formed by connecting the vertices of the adamantane
centers, following four unit vectors pointing in the directions of a
tetrahedron. Since for the lower diamondoids adamantane, diamantane, and
triamantane, the arrangement of their cages is evident, usually their dualist
codes are not used. In branched cases, the codes for the branch are placed
in parentheses, as indicated for [121(2)34] and [12(12)34]heptamantane.

assemble adamantane units in such a fashion that their dualist

graphs form cycles.
In the following, we will therefore briefly introduce the different
types of polymantanes proposed (Balaban and Schleyer, 1978),
which are based on whether their dualist graphs are acyclic (i.e.,
linear or containing branches), or whether they contain cycles.
In the case of polymantanes whose dualist graphs are acyclic,
the authors (Balaban and Schleyer, 1978) have proposed the term
“catamantanes” and “perimantanes” for molecules that contain
cycles. For the latter, depending on whether the cycle in the
dualist graph is composed of more than six vertices, the authors
26 Structure, Nomenclature, and Symmetry of Diamondoids

1. Acyclic: Catamantanes 2. Cyclic

(a) Perimantanes

[1212]pentamantane [1(2,3)4]pentamantane [12312]hexamantane

(b) Coranamantanes

[12(3)4]pentamantane

[121231212]decamantane

Figure 2.10 Classification of polymantanes according to their dualist

graphs. The two main groups are those whose dualist graph is acyclic and
those that contain cycles. If the vertices in a cycle of the dualist graph
contain more than six C atoms, the molecule is attributed to the class of
coronamantanes. The classification and examples are taken from Balaban
and Schleyer (1978). The dashed line indicates the link between the first
and the last cage; in the notation of the dualist graph, this is not written
explicitly since it becomes evident from the sequence of the dualist graph
notation.

have introduced the designation coronamantane. Examples of

catamantanes, perimantanes and coronamantanes are displayed in
Fig. 2.10. Just as a note, so far no coronamantanes have been
described experimentally (Balaban, 2012).
For the sake of completeness, we summarize in Table 2.1 the
dualist graph codes, point group symbols, chemical formulae, and
total number of structures of polymantanes for n = 1 to 6. In
this table, enantiomerism is not taken into account. As can be
seen from Table 2.1, all the lower diamondoids (n = 1 to 3)
possess only one structural isomer. Triamantane has 3 (4, if one
Table 2.1 List of polymantanes for cage numbers n = 1 to 6 (adamantane to hexamantane), their dualist codes, point
group symbol, chemical formula, and total number. C: dualist code; S: point group symbol; F: chemical formula; NP:
number of polymantanes, not taking into account enantiomers (Balaban and Schleyer, 1978). In the case of the regular
and irregular catamantanes, the indicated chemical formulae correspond to both linear and branched diamondoids.

Catamantanes Perimantanes
Regular Irregular Irregular

Linear Branched Linear Branched Cyclic

n C S F C S C S F C S C S F NP
1 Td C10 H16 1
2 1 D3d C14 H20 1
3 12 C 2ν C18 H24 1
4 121 C 2h C22 H28 1(2)3 C 3ν 3
123 C2
5 1212 C 2ν C26 H32 12(1)3 C1 7
1213 C1 12(3)4 Td 1231 Cs C25 H30
1234 C2
6 12121 C 2h C30 H36 121(2)3 C1 12132 C1 C29 H34 12(1)31 Cs 12312 D3d C26 H30 24
12123 C1 12(1)32 C1
12131 C1 121(3)4 Cs
12134 C1 12(1)34 C1 12314 C1 123(1)2 C1
12321 C1 12(1,3)4 C1 123(1)4 C1
12324 C2 12(3)12 Cs 12(3)41 Cs
12341 C2 1(2)3(1)2 C 2h
1(2)314 C1
12(3)14 C1
Nomenclature and Classification of Diamondoids

1(2)3(1)4 C2
27
Table 2.2 List of heptamantanes (n = 7) with their dualist codes, point group symbol, chemical formula and total number. C:
Dualist code; S: Point group symbol; F: Chemical formula; NP: Number of polymantanes, not taking into account enantiomers
(Balaban and Schleyer, 1978)

Catamantanes Perimantanes
Regular, C34 H40 Irregular Irregular

Linear Branched Linear Branched Cyclic

n C S C S C S F C S F C S F NP
7 121212 C 2ν 1212(1)3 C1 121231 C1 C33 H38 12(12)31 C1 C33 H38 121321 Cs C30 H34 88
121213 C1 121(2)31 C1 121323 Cs 121(2)32 C1 123124 Cs
121232 C1 1212(3)4 Cs 121324 C1 1213(1)2 C1
121234 C1 121(2)34 C1 121341 C1 12(1)3(1)2 C1
121312 C1 12(12)34 Cs 123132 C1 12(1)314 C1
121314 C1 121(2,3)4 Cs 123134 C1 12(1)3(1)4 C1
28 Structure, Nomenclature, and Symmetry of Diamondoids

121342 C1 1213(1)4 C1 123142 C1 12(1)321 C1

121343 C2 121(3)21 C1 123143 C2 C32 H36 1213(2)4 C1
123214 C1 121(3)23 C1 123421 Cs C33 H38 12(1)341 C1
123231 Cs 121(3)24 C1 12(13)41 Cs
123234 C2 12(1)324 C1 12(1,3)41 Cs
123241 C1 12(1)3(2)4 C1 121(3)42 C1
123412 C2 12(13)32 C3 12(1)342 C1
12(13)34 C1 12(13)43 C1
121(3)41 C1 123(1)23 C1
 12(1,3)42 C1 1(2)31(2)3 Cs
121(3)43 C1 123(1)24 C1
12(1,3)43 C2 1(2)3124 C1
12(3)1(2)3 C1 123(1,2)4 C1
12(3)124 C1 1(2)31(2)4 C1
12(3)1(2)4 C1 12(3)132 C1
1(2)3(1)24 C1 1231(3)4 C1
1(2)3(1,2)4 Cs 12(31)41 C 3ν C32 H36
1(2)3132 C1 123(1)42 C1
12(3)134 C1 12(3)142 C1 C33 H38
1(2)3134 C1 1(2)3(1)42 C1
12(3)1(3)4 C1 123(1)43 C1
1(2)31(3)4 C2 123(2)14 C1
1(2)3142 C1 1234(1)2 C1
1232(1)4 C1 12(3)4(1)2 C1
123(2)41 C1 1(2)34(1)2 C 2ν C32 H36
12(3,4)12 C 2ν
123(4)21 C1
Nomenclature and Classification of Diamondoids
29
30 Structure, Nomenclature, and Symmetry of Diamondoids

takes also into account chirality of the [123]tetramantane). In the

case of pentamantane, (n = 5), one has 7 possible structural
isomers, hexamantane (n = 6) has 24, and heptamantane (n = 7)
has 88 (Balaban and Schleyer, 1978).
From pentamantane onwards, one can also see that it is possible
to form diamondoids that do not possess the same molecular mass.
Table 2.1 also lists the point groups the diamondoids belong to, and
they will be discussed more in detail in Section 2.5.

2.4.3 Regular and Irregular Polymantanes

From the treatment in the previous sections on the structure of
the diamondoids and their nomenclature using dualist graphs, one
can see that the combinations of arranging the adamantane units
increase rapidly for n > 4.
On fusing an additional adamantane unit onto an diamondoid
consisting of n cages, two types of an n + 1 diamondoid can be
formed. The first type is characterized by the chemical formula
C4n+6 H4n+12 and it can be obtained conceptually by replacing three
axial hydrogen atoms bonded to the same cyclohexane ring. It can
be assumed by addition of a trimethylenemethane group, resulting
in the net addition of C4 H4 . Diamondoids of this type are called
regular n-catamantanes, and for the same cage number n, they are
isomeric (Balaban and Schleyer, 1978).
The other types of diamondoids, also named irregular cataman-
tanes, result from the addition of Cx H y with x < 4 and y < 4.
An example of this is shown in Fig. 2.11b, which illustrates the
formation of [1231]pentamantane from [123]tetramantane by the
addition of C3 H3 . The necessary and sufficient conditions for a
catamantane to be irregular is to have a code with at least two
identical digits separated by any two other digits (not taking
into account branches, that is, digits inside parentheses). For
example, the sequences a1bc1d . . ., . . . 2ab2c . . ., ab3(b)cd3 . . . ,
. . . abc4(a)b(d)a4d . . . , and . . . ab1(a)bc(1)d . . . are examples of
dualist codes of irregular catamantanes (here, the variables a–d
stand for the digits 1 to 4).
For diamondoids up to and including tetramantane, the chemical
formula of all possible isomers is C4n+6 H4n+12 . Starting with penta-
 Nomenclature and Classification of Diamondoids 31

a b

[0] [1] [1] [12] [123] [1231]

Figure 2.11 Formation of regular and irregular catamantanes. (a) Addition

of a C4 H4 group results in diamondoids with the chemical formula
C4n+6 H4n+12 , for example, diamantane from adamantane and triamantane
from diamantane. (b) For the case where the added fragment is Cx H y with
x < 4 and y < 4, (e.g., C3 H3 for [123]tetramantane to [1231]pentamantane),
so-called irregular catamantanes are formed.

mantane, n = 5, one can obtain an isomer of different molecular

mass, [1231]pentamantane, with chemical formula C4n+5 H4n+10 .
Continuing the series of diamondoids for n ≥ 6, the number of
isomers increases, with a new group having the generic chemical
formula C4n+2 H4n+6 . With each increment of n by 1, new groups are
added to the diamondoid family: C4n+4 H4n+8 for n ≥ 7, C4n+1 H4n+4
for n ≥ 8, C4n−2 H4n for n ≥ 9, C4n−5 H4n−4 for n ≥ 10, and finally
C4n−3 H4n−2 for n ≥ 11.
A list of these different diamondoid groups for n = 1 to 12
(dodecamantane) and their respective classes of molecular weights
is summarized in Fig. 2.12.

2.4.4 Formula Partition Periodic Table

Extending the original work on the dualist graph-based classifi-
cation of diamondoids, Balaban has proposed a formula partition
periodic table of regular diamondoid valence isomers, that is,
regular catamantanes that have the molecular formula C4n+6 H4n+12
(Balaban, 2012).
As will be shown the following chapters, the position of the
C atoms and their connectivity with other C atoms of the diamondoid
structure influence the reactivity. While the dualist graph naming
32 Structure, Nomenclature, and Symmetry of Diamondoids

Group n 1 2 3 4 5 6 7 8 9 10 11 12 …
1 C4n+6H4n+12 136 188 240 292 344 396 448 500 552 604 656 708
2 C4n+5H4n+10 330 382 434 486 538 590 642 694
3 C4n+2H4n+6 342 394 446 498 550 602 654
4 C4n+4H4n+8 420 472 524 576 628 680
5 C4n+1H4n+4 432 484 534 588 640
6 C4n−2H4n 444 496 548 600
7 C4n−5H4n−4 456 508 560
8 C4n−3H4n−2 534 586
…

Regular, linear catamantanes

Catamantanes and perimantanes

Figure 2.12 Listing of molecular weights of diamondoids from adamantane

(n = 1) up to dodecamantane (n = 12). The columns n = 1 to 12
denote the number of cages, while the rows 1 to 8 indicate different
diamondoid groups that result from different possible cage arrangements.
Group 1 diamondoids (C4n+6 H4n+12 ) stand for regular, linear catamantanes,
while diamondoids belonging to higher groups contain regular branched
catamantanes, irregular linear and branched catamantanes, and irregular
cyclic perimantanes (cf. Tables 2.1 and 2.2).

scheme proposed by Balaban and von Schleyer (Balaban and

Schleyer, 1978) is more straightforward compared to the official
IUPAC names, there are also some drawbacks.
For example, it is not easy to distinguish stereoisomers and the
position of C and H atoms, and furthermore, it does not allow to
deduce the number of secondary, tertiary and quaternary C atoms
(i.e., whether a C atom is connected to two, three or four other
C atoms) directly.
Therefore, in addition to the dualist graph based nomenclature
of diamondoids, additional schemes have been developed to classify
diamondoids.
Figure 2.13 displays the molecular structure of a series of
diamondoids, with the colors of the C atoms indicating the number
 Nomenclature and Classification of Diamondoids 33

Ada Dia Tria [121]tetra [123]tetra [1(2)3]tetra

[1212]penta [1234]penta [1213]penta [1231]penta [1(2,3)4]penta

C atom:
secondary (2º)
tertiary (3º)
quarternary (4º)

[12(3)4]penta [12312]hexa [121231212]deca

Figure 2.13 Molecular structures of diamondoids and C atoms coordina-

tion. The different types of C coordination are indicated by colors: linked
to two C atoms, secondary (2◦ , gray); linked to three C atoms, tertiary (3◦ ,
blue); linked to four C atoms, quaternary (4◦ , red).

of other C atoms they are connected to: Four (quaternary, 4◦ ),

three (tertiary, 3◦ ), or two (secondary, 2◦ ). Both adamantane and
diamantane only contain 3◦ or 2◦ C atoms. Then, starting with
triamantane, one obtains diamondoids that also contain 4◦ C atoms,
that is, it is the first diamondoid with a bulk-coordinated C atom.
As will be shown in a subsequent chapter, the coordination of
C atoms in the diamondoid framework has a large influence on their
reactivity and is therefore paramount for applications involving
their functionalization.
Based on the coordination number of C atoms, additional classi-
fication schemes of diamondoids have been developed. One consists
in subdividing the chemical formula of the diamondoids into
subgroups that indicate the C coordination number: C Q (CH)T (CH2 ) S .
Here, the subscripts Q, T , and S indicate the number of 4◦ , 3◦ , and 2◦
C atoms, respectively. Table 2.3 lists the molecular formulae and the
corresponding partitions for adamantane, diamantane, triamantane,
and tetramantane.
34 Structure, Nomenclature, and Symmetry of Diamondoids

Table 2.3 Partition table of regular catamantanes (chemical formula

C4n+6 H4n+12 ); the first row in the table is the chemical formula of the
diamondoid separated into quaternary, tertiary, and secondary groups; the
second row lists the number of the groups, and the third is the dualist
degree partition (after (Balaban, 2012))

Zero branches One branch

Number of cages n Molecular formula C atoms C atoms
Partition Partition
1 C10 H16 (CH)4 (CH2 )6
0−4−6
0, 0, 0, 0

2 C14 H20 (CH)8 (CH2 )6

0−8−6
1, 1, 0, 0

3 C18 H24 C(CH)10 (CH2 )7

1 − 10 − 7
2, 1, 0, 0

4 C22 H28 C2 (CH)12 (CH2 )8 C3 (CH)10 (CH2 )9

2 − 12 − 8 3 − 10 − 9
2, 2, 0, 0 3, 0, 1, 0

2.5 Molecular Symmetry and Crystal Structures

of Diamondoids
In this section, we give a brief overview over the molecular
symmetry of diamondoids and the crystalline structures they
adopt in the solid phase. As we will see in the chapter on
vibrational spectroscopy of diamondoids, knowing the symmetry of
the molecule can help in the interpretation of spectra and assigning
peaks. Conversely, knowing the rules for Raman or IR active
vibrational modes can help to guess the symmetry of the molecule
under investigation. In addition, we also briefly list the known
crystal structures that diamondoids accommodate in the solid
phase.
 Molecular Symmetry and Crystal Structures of Diamondoids 35

2.5.1 Molecular Symmetry of Diamondoids

As will be explained in more detail, one convenient means to
characterize diamondoids is by vibrational spectroscopy techniques,
namely infrared (IR) and Raman spectroscopy. These techniques
probe the different vibrational modes of the molecules. However,
while both IR and Raman measurements are relatively easy to carry
out, the interpretation of the spectra is not always straightforward.
In order to understand in more detail the different types of
spectral features that can be expected, to determine whether certain
vibrational modes are either IR or Raman active, and to assign them
to specific vibrational modes, it is helpful to know the symmetry
groups and elements of the different diamondoids. Depending on
the symmetry of a given diamondoid, the features in the spectra
will change. In particular, diamondoids of higher symmetry will
show less distinctive peaks compared to diamondoids having lower
symmetry.
Here, we will not go too much into details of molecular symmetry
and refer the interested reader to relevant textbooks of this topic.
The main symmetry groups diamondoids belong to are C 1 (i.e., no
symmetry element except identity, E ), C 2 , C 2ν , C 2h , C s , C 3ν , D3d , and
Td (Balaban and Schleyer, 1978; Dahl et al., 2003a).
As an example, we show the molecular structures and their
symmetry elements of diamondoids ranging from adamantane
to tetramantane in Fig. 2.14. The most symmetric diamondoids
are adamantane (symmetry group Td , cf. Fig. 2.14). The only
another diamondoids belonging to the same symmetry group
are [1(2, 3)4]pentamantane and [1231241(2)3]decamantane (the
“adamantane-of-adamantanes” or “superadamantane”). All the other
diamondoids are of lower symmetry, either completely lacking any
symmetry element (C 1 ) or possessing only one axis of rotation C 2 .

2.5.2 Crystal Structures of Diamondoids

In this part, we briefly discuss the crystalline structure of diamon-
doids in the solid phase. While from all the lower diamondoids, the
crystal structures are known, in the case of higher diamondoids,
only those that have been obtained in larger quantities could
36 Structure, Nomenclature, and Symmetry of Diamondoids

Improper axis Mirror plane

C2 / C3 Rotation axis
Adamantane: Td Diamantane: D3d Triamantane: C3v

E, 8C3, 3C2, 6S4, 6σd

Inversion
center

[121]Tetramantane: C2h [123](P)skew-Tetramantane: C2

Figure 2.14 Examples of diamondoids, their molecular structures,

and symmetry elements. Typically, diamondoids belong to point
groups Td (adamantane), D3d (diamantane), C 2ν (triamantane), C 2h
([121]tetramantane), and C 2 ([123](P)skew-tetramantane).

be characterized. Table 2.4 lists the known crystal structures of

diamondoids and illustrates the crystal structures of adamantane
and [1(2, 3)4]pentamantane in Fig. 2.15. Adamantane crystallizes
in the face-centered-cubic (fcc) structure (space group F43m),
while [1(2, 3)]pentamantane is orthorhombic (P21 /m). In these
crystalline structures, the diamondoid cages are only linked by
van der Waals forces, but as will be shown in the next chapter, the
regular molecular structure of especially the lower diamondoids
leads to much higher thermals stability and melting points com-
pared to alkanes of comparable molecular masses.
In the case of single-crystalline adamantane, two types of struc-
tures have been reported: P42c (triclinic) for temperatures below
–65◦ C, and a disordered structure with space group Fm3m
 Molecular Symmetry and Crystal Structures of Diamondoids 37

Table 2.4 Listing of diamondoids with know crystal structure and

corresponding space groups. The symbols in bold represent the space
group, while the codes in parentheses are the Schönflies symbols

Name Molecular formula Dualist code Crystal structure

Adamantane C10 H16 [0] Fm3m (Oh )

Diamantane C14 H20 [1] Pa3 (Th6 )

24
Triamantane C18 H24 [12] Fddd (D2h )

Tetramantanes C22 H28 [121] P21 /m (C 2h2

)
[123] P1 (C 11 )

Pentamantanes C26 H32 [1212] P21 21 21 (D24 )

16
[1(2, 3)4] Pnma (D2h )
[12(3)4] P21 /m (C 2h 2
)
[1213] P1 (C i1 )

16
Hexamantanes C26 H30 [12312] Pnma (D2h )

3
Heptamantanes C30 H34 [121321] C2/m (C 2h )

c
c

0 a
b
a b

Adamantane [1(2,3)4]pentamantane

Figure 2.15 Crystal structures of adamantane (face-centered-cubic, space

group F43m), and 1(2, 3)4pentamantane (orthorhombic, Pnma). The
individual diamond cages in the crystals are only linked by relatively weak
van der Waals forces.
38 Structure, Nomenclature, and Symmetry of Diamondoids

(Nordman and Schmitkons, 1965), contrary to earlier reports that

assigned the structure to be cubic (space group F43m).

2.6 Differences between Diamondoids and

Nanodiamonds
It might be in order to make a clear distinction between nano-
diamonds and diamondoids. Although with increasing cage number,
diamondoids become of similar size as nanodiamonds, (typical size
2–6 nm), it might be better to make a distinction between these two.
Usually the term “nanodiamond” is used in different contexts and for
a variety of structures that contain diamond nanocrystals, present,
for instance, in interstellar dust and meteorites, diamond particles
nucleated in the gas phase or on substrates, and nanocrystalline
films (Shenderova et al., 2002). Typically, nanodiamonds may also
possess a wide range of size scales, size distributions and also
consist of mixtures containing other elements such as nitrogen
and oxygen (i.e., doped nanodiamonds). In contrast, diamondoids
“are chemically well defined, of high purity, and structurally well
characterized” (Schwertfeger et al., 2008).
In particular, in the case of nanodiamonds, while their core is
composed of sp3 -bonded carbon, their surface can be terminated
by many different functional groups or consist of reconstructed
surfaces formed by sp2 -hybridized graphitic networks (Raty and
Galli, 2003). It has also been found that different fractions of
detonation nanodiamond possessing different particle sizes also
have varying surface compositions, namely different concentrations
of hydrogen- or oxygen-containing groups (Larionova et al., 2006).
Especially the fractions of smaller nanodiamonds with polar oxygen-
containing groups (C−OH, C−O−C, C−O) lead to more facile
dispersion in water.
In contrast, diamondoids have a well-defined structure and the
sp3 bonded carbon cages are terminated by H atoms or other func-
tional groups. For this reason, diamondoids are also called diamond
molecules or diamond hydrocarbons. Figure 2.16 illustrates the
difference in the structure and surface terminations of diamond
 Differences between Diamondoids and Nanodiamonds 39

a b
O

[1231241(2)3]decamantane

Nanodiamond

Figure 2.16 Comparison between structures nanodiamonds and diamon-

doids. (a) Example of nanodiamond consisting of a diamond core and
surface that contains functional groups. (b) Structure of superadamantane;
in contrast to nanodiamonds, the surface terminations are well defined and
can consist of hydrogen atoms or other functional groups.

clusters and nanodiamonds on the one hand, and diamondoids

on the other. Diamond clusters possessing not complete hydrogen
terminations are also called bucky diamond (Raty et al., 2003) due
to the resemblance of their reconstructed surface to the one of
fullerenes.
Therefore, despite advances in their purification and function-
alization, the major disadvantage of nanodiamonds remains their
nonuniform size and size distribution (Schwertfeger et al., 2008). In
contrast, as will be explained in more detail in the following sections,
diamondoids are more similar to molecules, possessing well-defined
structure, size, and composition.
As mentioned briefly in the previous section, most current
applications of nanodiamond synthesis are based on detonation
techniques, that was discovered in the 1960s (DeCarli and Jamieson,
1961; Dolmatov et al., 2004). However, once obtained, they have
to be purified using strong (50%–99%) nitric acid at temperatures
of 80◦ C–180◦ C. The chemical purification and oxidation steps
are the most expensive and complex stages in the fabrication of
nanodiamonds.
40 Structure, Nomenclature, and Symmetry of Diamondoids

The growth of nanodiamonds by detonation synthesis is thought

to occur by several mechanisms and in several stages. A recently
proposed growth mechanism (Dolmatov et al., 2013) occurs in the
following steps:
(1) Decomposition of the precursor and carbon source trinitro-
toluene (TNT) into basic radicals and radical-like dimer C2
and CO3 , decomposition of hexogen molecules into C2 and of
benzotrifuroxane molecules into C2 ;
(2) Formation of cyclohexane from C2 or immediately of radical
adamantane molecules;
(3) Interaction of diamond-like core (adamantane radical) with
methyl and other monocarbon radicals; and
(4) Growth of detonation nanodiamond particles like in a CVD
process.
In the following chapter, we discuss the chemical and physical
properties of diamondoids in more detail, before introducing
current and possible future applications of diamondoids.
Chapter 3

Chemical and Physical Properties and

Characterization of Diamondoids

This chapter builds on the previous one but goes more into the
details of the molecular structure, chemical, thermodynamic, and
physical properties of diamondoids. The first part of the chapter
is devoted to the molecular structure of diamondoids, especially
the exact lengths of the bonding angles and bond lengths between
C and H atoms. We also discuss the electronic structure of the
diamondoids more in detail, as this will permit us to understand the
variation of the bandgaps of both H-terminated and H-functionalized
diamondoids. The other parts are devoted to the thermodynamic
properties, including solubilities both in organic solvents, gases, and
supercritical fluids. Furthermore, we present the physical properties
of diamondoids, that is, the variation of their bandgaps as a function
of size and functionalization.

3.1 Chemical Properties

In this section, we give an overview of the chemical properties of
diamondoids, including their molecular structure. In the first part

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
42 Chemical and Physical Properties and Characterization of Diamondoids

HOMO LUMO

Figure 3.1 Molecular structure of adamantane and representation of its

HOMO and LUMO. The red orbitals represent the negative part of the
wavefunction and the blue the positive (the isosurface values have been set
to ±0.04).

of this paper, we will first discuss in more detail the electronic

structure of diamondoids, in particular adamantane. In addition to
the presentation of the chemical properties, we will describe the
reactivities of diamondoids and the implication of these for the
formation of new compounds.
Figure 3.1 presents a ball-and-stick model of adamantane, and
the shape of the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO), as obtained by
ab initio calculations. As can be seen in this figure, the HOMO of
adamantane is mainly localized around the C−C and C−H bonds.
Because of the hydrogen terminations of diamondiods, they are
highly nonpolar. As will be shown in more detail in a later section,
the solubility of diamondoids in typical organic solvents is limited.
So far, because with a few exceptions, especially larger diamon-
doids are not readily available, many of the chemical properties of
diamondoids have not been measured directly, but rather have been
predicted using computational chemistry approaches. Consequently,
in the present text, we will also make frequent reference to such
work from the scientific literature.
A detailed study on the structure and symmetry of diamondoids
from adamantane to decamantane (adamantane-of-adamantane or
 Chemical Properties 43

superadamantane) (Shen et al., 1992) showed that for all levels of

theories investigated (molecular mechanics, semi-empirical, and ab
initio), that the C−C bonds in these molecules were longer than
in bulk diamond (154.45 pm). Their simulations also showed very
good agreement with experimental values of diamondoids that were
available, that is, adamantane to triamantane.
Following the isolation and synthesis of the lower diamondoids
in the 1950s and 1960s, their structures were investigated by X-ray
diffraction (XRD) by several groups. The first study on the crystal
structure of diamantane was carried out in 1965 (Karle and Karle,
1965).
In the case of triamantane, XRD analysis and Raman spectroscopy
measurements indicated a change in the crystal structure, which
was also confirmed by differential thermal analysis (DTA) (Jenkins
and O’Brien, 1981). The onset of this transition was found to occur
at about 20.5 ± 0.5◦ .
Following its synthesis (cf. Chapter 6), the crystal structure
of antitetramantane was investigated using XRD by (Roberts and
Ferguson, 1977).
Recently, the effect of pressure on the crystal lattice of
[121] Tetramantane has been investigated (Yang et al., 2014). The
authors found that for pressures above 13 GPa, the monoclinic
P 21 /n structure changes to a triclinic P1 structure and the
transition to the new structure was complete at a pressure of 16 GPa.
The change in crystal structure displayed a large hysteresis and
in addition, the appearance of a new phase with space group Pc,
existing down to a pressure of 4 GPa, was observed when reducing
the pressure. The phase change as a function of pressure was
attributed to a change in the intermolecular packing, that is, the
initially loosely packed unit cell became highly compacted at high
pressure. The variation of the XRD spectra as a function of pressure
up to 16 GPa is shown in Fig. 3.2.
While the structure of the lower diamondoids has been in-
vestigated both experimentally and numerically, the structure of
larger diamondoids was long not possible because of insufficient
computing power. In recent year, also the structural properties
of larger diamondoids have been investigated, such as the one of
cyclohexamantane (Richardson et al., 2006).
44 Chemical and Physical Properties and Characterization of Diamondoids

λ = 0.4246 Å
19.1

16.1 P1

14.2
P1, P21/n
13.0

11.2
Intensity (arb. units)

10.2

8.6

7.6

6.4 P21/n
4.4

3.2

2.4

1.7

0.4

4 6 8 10 12 14
2θ (º)

Figure 3.2 Variation of the crystal structure of [121]tetramantane as a

function of pressure. The curves vary from p = 0.4 to 19.1 GPa. The lines
on the right indicate the regions of the P21 /n and P1 phases. Between 13
and 16 GPa, P1 and P21 /n coexist, whereas for pressures above 16 GPa, only
P1 remains. Data adapted from Yang et al. (2014).

3.1.1 Thermodynamic Properties

In this section, we discuss the main thermodynamic properties of
diamondoids. Up to now, only a few diamondoids are available in suf-
ficiently large quantities that allow such characterization, therefore
the discussion focuses mainly on adamantane and diamantane.
In addition to these two diamondoid homologues, the stan-
dard enthalpies of formation of a few adamantoid compounds
have also been investigated in detail. These included 1- and
2-methyladamantane; 2,2- and 1,3-dimethyladamantane; 1,3,5-
trimethyladamantane; and 1,3,5,7-tetramethyladamantane (Steele
and Watt, 1977). In general, the enthalpies of formation increase
 Chemical Properties 45

with increasing number of substitution from −H f◦ = 242.7 ± 1.7

and 224.7 ± 1.7 kJ.mol−1 for 1- and 2-methyladamantane to 378.7 ±
3.8 kJ.mol−1 for 1,3,5,7-tetramethyladamantane.
The phase diagrams of adamantane and diamantane are dis-
played in Fig. 3.3. In the case of adamantane (Fig. 3.3a), three
different states—solid, liquid, and gas—can be observed whereas for
diamantane (Fig. 3.3b), three distinct different solid phases can be
identified.
In addition to the different phases, both substances also exhibit a
critical point.
At −65◦ C (≈209 K), a phase transition occurs in adaman-
tane (Nordman and Schmitkons, 1965). The phase change involves a
transition from the face centered cubic room-temperature structure
to a tetragonal structure, space group P 4̄21 c, with a = 660 pm,
c = 881 pm and Z = 2.
The low-temperature cell is related to the cubic cell by atetra 
acubic /2 and ctetra  acubic . A single-crystal X-ray study of the
low-temperature phase at −110◦ C shows the arrangement of the
molecules to be unchanged except for a 9◦ tilt about the c axis.
The authors also found that at room temperature, the structure
of adamantane is not well ordered and supports a structure that
belongs to the space group F m3m.

3.1.2 Chemical Stability

In the following, we will also briefly discuss the stability of
diamondoids with respect to their size and in comparison to
nanodiamondoids, and also as a function of their terminations, that
is, the hydrogen content.
The structures of diamonds and the consequence of it on
properties has been investigated since the earliest synthesis (Fort
and Schleyer, 1964)
Since the discovery of diamond clusters of 3–5 nm in size from
detonation synthesis and observation in meteorites, their stability
with respect to bulk diamond has been investigated by several
groups and suggested that such small diamond clusters could be
more stable than graphite at ambient conditions (Badziag et al.,
1990).
46 Chemical and Physical Properties and Characterization of Diamondoids

105
a Liquid
104 ∆Hg = 13.1 kcal g-1mol-1
(Clausius - Clapeyron) Solid
103
Estimated
critical point
102 Boyd correlations
Pressure (kPa)

1 ∆Hv = 9.28 kcal g-1mol-1

10 (Clausius - Clapeyron) Cullick et al.
correlation
100

10-1 Vapor ∆Hs = 14.3 kcal g-1mol-1

(Clark, 323 K)
10-2 Triple point: 543 K

10-3 Static cell

10 -4 DSC measurements
CO2 solubility-based
10-5
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
T-1 ×103 (K-1)

105
b ∆HS3-L = 2.2 kcal g-1mol-1 (DSC)
104
Estimated Liquid ∆HS2-S3 = 2.1 kcal g-1mol-1 (DSC)
critical point
Solid 3 ∆HS1-S2 = 1.1 kcal g-1mol-1 (DSC)
103 Solid 2
102 Solid 1
∆Hv = 11.5 kcal g-1mol-1
Pressure (kPa)

101 (DSC), 543 K

∆HS1 = 22.93 kcal g-1mol-1
∆Hv = 11.3 kcal g-1mol-1 (Clark, 313 K)
100 Vapor
(Clausius - Clapeyron)

10-1 Cullick et al.

Correlations
Triple points: S3-L-V 516 K
10-2 S2-S3-V 442 K
S1-S2-V 411 K
10-3
Vapor pressure apparatus
10-4 DSC measurements
CO2 solubility-based
10-5
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
T-1 ×103 (K-1)

Figure 3.3 Phase diagrams of adamantane and diamantane, including the

critical points. (a) Adamantane and (b) diamantane, which contains three
different solid phases. Data adapted from Reiser et al. (1996).

The energy of formation E f can be defined as:

E f = E tot − μC NC − μH NH − E vib (3.1)
with E tot the total energy, μC , μH and NC , NH are the numbers and
chemical potentials of carbon and hydrogen atoms, and E vib is the
vibrational energy.
 Chemical Properties 47

3.0 3.0

2.5 2.5

2.0 2.0
Ef (eV Atom-1)

Ef (eV Atom-1)
1.5 1.5

1.0 1.0
μ0 μ0
Bare
0.5 (100) + (111) reconstructed 0.5
(100) reconstructed
Completely hydrogen
terminated
0.0 0.0
20 19 18 17 16 15 20 19 18 17 16 15
μH (eV) μH (eV)

Figure 3.4 Comparison of the formation energy of diamond of different

sizes and with different hydrogen coverage. (a) C66 diamond cluster. (b)
Diamond cluster C275 (not shown). The energy is plotted as a function of
the hydrogen chemical potential (μH ), which can be attributed to different
preparation conditions. Data adapted from Raty and Galli (2005). The line
at μ0 = −15.27 eV is the formation energy of methane, whose molecular
structure is also shown for size comparison. For better visibility, the
hydrogen terminations of the nanodiamonds are colored in red. Note:
The diamondoid structures depicted in the figure do not correspond to the
actual, optimized structures.

The computed difference in formation energy per carbon atom

() can be assumed to depend only on the number of surface carbon
atoms. With this assumption, the difference in energy becomes
   
E f, bare 3/2 E f, stable 3/2
= − (3.2)
NC NC
It has be found (Raty and Galli, 2005), that  is almost linear with
the particle diameter, as shown in Fig. 3.4, where the variation of E f
as a function of the chemical potential of hydrogen, μH is presented.
Figure 3.5 shows the difference in the formation energy
between nanodiamonds possessing fully reconstructed surfaces 
(in eV1.5 /Carbon), and the most stable structures with hydrogen
48 Chemical and Physical Properties and Characterization of Diamondoids

5
mH = −16.5 eV
mH = −16.0 eV
mH = −15.5 eV
mH = −15.0 eV
mH = −14.5 eV
4

3
eV 1.5 Carbon

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Diameter nm

Figure 3.5 Variation in formation energies of nanodiamonds as a function

of surface reconstruction and size. The differences in formation energies
to the power 3/2, , are between those of nanodiamonds possessing fully
reconstructed surfaces and the most stable nanodiamond structure, for
a given value of the hydrogen chemical potential μH . The shaded gray
area for particle sizes between 2 and 3 nm indicates the domain where
nanodiamonds with bare unreconstructed surfaces become more stable
than those with hydrogen at their surface. Data adapted from Raty and Galli
(2005).
 Chemical Properties 49

terminations. As can be seen from the figure, the difference

decreases with diamond size and reaches zero for sizes in the range
between 2 and 3 nm.
These calculations show that for sizes above 3 nm, nan-
odiamonds with reconstructed surfaces are more stable than
nanodiamonds possessing complete hydrogen terminations.
The size of nanodiamonds and their stability is also crucial for
biological applications. By performing MD simulations of annealing
in vacuum and in the presence of oxygen, it was found that diamond
clusters of cubic or cuboctahedral shapes with over ∼250 atoms
can survive long-term annealing up to temperatures of 1500 K.
The primary role of oxygen is the saturation of surface carbon
atoms and the etching of the graphitic part, that is, to increase the
sp3 ratio. The results showed that {100}-faceted nanodiamonds
with sizes as small as 1 nm can be kinetically stable up these
temperatures (Kaviani et al., 2013).
Figure 3.6 shows computationally obtained relative stabilities
(H 298 ) of tertiary diamondoidyl cations, which are obtained from
the reaction of the 1-adamantyl cation (1 − Ad+ ) and a given

0
Relative enthalpies of formation ΔH298 (kcal mol–1

0.0

−1.6

−5 −4.7
−5.2
−6.0 −6.1

−7.6 −7.8
−8.0
−8.4 −8.4
−9.4−9.4 −9.1 −9.1
−10 −9.8 −9.5
−10.1 −10.3
−10.8 −10.7 −10.7 −10.7
−11.3
−11.8

−15

Figure 3.6 Relative stabilities of tertiary diamondoidyl cations in compar-

ison to the 1-adamantyl cation. The values of H 298 are obtained from
Eq. 3.3. Data adapted from Fokin et al. (2005).
50 Chemical and Physical Properties and Characterization of Diamondoids

diamondoid (Fokin et al., 2005):

1 − Ad+ + diamondoid AdH + tert-diamondoidyl+ (3.3)

3.1.3 Solubility of Diamondoids in Gases, Organic

Solvents, and Supercritical Fluids
The pressure-temperature conditions in the natural gas production
or oil exploration often lead to the formation of solids, which then
clog the pipes, which leads to delays and ultimately production
losses. Therefore, for the exploration of diamondoids from natural
gas or oil reservoirs or for their further treatment—separation
and purification—by organic chemistry, knowing how well they
are soluble in a given fluid is essential. This section contains an
overview of most of the currently available data on the solubility of
diamondoids in gases, organic solvents, and supercritical fluids.

3.1.3.1 Solubility in organic solvents

Diamondoids often clog pipes in oil or gas reservoirs and therefore,
to mitigate this problem, it is essential to know the solubility limits
of diamondoids in various fluids and for different temperature and
pressure conditions.
Several research groups have studied the solubility of diamon-
doids in various organic solvents, and both atmospheric and high-
pressure conditions, including the supercritical state. For example,
Smith and Teja (Smith and Teja, 1996) have investigated the
solubility of adamantane in several organic solvents. Figure 3.7
displays the variation of the solubility y2 of adamantane and
diamantane as a function of solvent density for CO2 , methane (CH4 ),
and ethane (C2 H6 ).
The solubility of several diamondoids and derivatives of dia-
mantane in typical organic solvents has also been studied (Chan
et al., 2008). The mass fraction solubilities (S) of diamantane,
triamantane, and tetramantane as a function of temperature are
listed in Table 3.1 (in the case of tetramantane, the solubility values
are those of four isomers).
In general, saturated diamondoids are more easily dissolved
in nonpolar solvents. For diamondoids that contain polar groups,
 Chemical Properties 51

Adamantane
CO2 333K
0.035 CH4 333K
C2H6 333K

0.030 Diamantane
CO2 333K
CH4 353K
0.025 C2H6 333K

0.020
y2

0.015

0.010

0.005

0.000
5 10 15 20
Solvent density (mol L-1)

Figure 3.7 Solubilities y2 (solid mole fraction) of adamantane and

diamantane in CO2 , CH4 , and C2 H6 as a function of solvent density. Data
compiled from Smith and Teja (1996) and Swaid et al. (1985).

for example, 1-hydroxyl diamantane or 1,6-dihydroxyl-diamantane,

they can also be dissolved in polar solvents.
In case the melting temperature Tm , the enthalpy of fusion H fus ,
and the activity coefficient γ2 of the solute are known, then the
52 Chemical and Physical Properties and Characterization of Diamondoids

Table 3.1 Experimental mass fraction solubility, S, of diamantane, tria-

mantane, and tetramantane in cyclohexane, ethyl acetate, toluene, acetone,
heptane, and 1-pentanol as a function of temperature T. Data adapted
from Chan et al. (2008)

100 w
T (K) Cyclohexane Ethyl acetate Toluene Acetone Heptane 1-Pentanol
Diamantane
283.15 4.336 0.555 2.790 0.274
293.15 5.430 0.820 3.976 0.412
303.15 6.827 1.191 5.132 0.633
313.15 9.144 1.495 7.148 0.905
323.15 12.259 2.413 9.520 1.425
333.15 14.945
343.15 19.022
Triamantane
273.15 5.396 0.396 3.802 2.842 0.600
298.15 9.553 1.010 7.642 6.503 1.272
323.15 15.492 2.120 14.314 10.651 2.725
348.15 26.012 5.175 26.152 17.564 5.436
Tetramantane
273.15 0.216 3.032 2.360 0.474
298.15 2.968 0.412 5.885 3.733 0.958
323.15 5.517 1.327 9.748 6.942 2.006
348.15 8.992 3.980 14.511 14.219 4.118

solubility can be estimated from

 
H fus 1 1
ln(γ2 x2 ) = − − (3.4)
R T Tm

where x2 is the mol fraction of the solute and R = 8.314462

J.mol−1 .K−1 is the universal gas constant.
The activity coefficients γ2 of the solute can be estimated from a
model such as the nonrandom two-liquid (NRTL) model:
  2 
G12 τ12 G21
ln(γ2 ) = x1 τ12
2
+ (3.5)
x2 + x1 G12 (x1 + x2 G21 )2

where G12 = exp(−α12 τ12 ), G21 = exp(−α12 τ21 ), and τ12 and τ21 are
interaction parameters.
 Chemical Properties 53

Solubilities of adamantane and diamantane have also been

measured in pressurized hot water up to 5 MPa, at temperatures
between 313 K and the solid-liquid-vapor triple point of the
solute (Karasek et al., 2008). Figure 3.9 illustrates the solubilities
of adamantane, diamantane, and a series of polycyclic aromatic
hydrocarbons in aqueous solutions as a function of temperature.
There have also been a few reports on the solubilities of
diamondoids in gaseous systems. However, because of the very small
solubilities (on the order of ∼10−4 ), measuring the concentrations
is very difficult and there are only a limited amount of experimental
data available. For adamantane and diamantane, a thermodynamic
data assessment test has been performed (Eslamimanesh et al.,
2011) to determine their solubilities in supercritical CO2 and
ethane.

3.1.3.2 Solubility in gases and supercritical fluids

Because of their high thermal stability and low volatility, diamon-
doids can be concentrated in the exploration of gas or oil reservoirs
and lead to clogging of pipes. To understand the conditions under
which diamondoids solidify and start clogging piping systems, the
solubility of diamondoids in high-pressure and supercritical fluids,
especially CO2 , has been investigated (Swaid et al., 1985).
Figure 3.8 displays the variation of the solubility of adamantane
in supercritical CO2 (scCO2 ), as a function of temperature, pressure,
and density.
As has been explained above, diamondoids cannot be readily
dissolved in polar solvents, unless the diamondoids contain polar
functional groups. Because of the low solubility, data in polar
solvents is difficult to measure, but the aqueous solubilities of the
two smallest diamondoids adamantane and diamantane have been
investigated by Karásek et al. (2008).
Figure 3.9 shows the solubilities of adamantane, diamantane, and
three polycyclic aromatic hydrocarbons (PAHs) in aqueous solutions.
The PAHs chosen for comparison are naphthalene (C10 H8 ), who has
the same number of carbon atoms as adamantane, and anthracene
and phenanthrene, who both have the same number of carbon atoms
as diamantane. As expected, the solubility of diamantane is much
54 Chemical and Physical Properties and Characterization of Diamondoids

100

80
Solubility (103 g cm-3)

60

40

20 343.0 K
362.5 K
382.0 K
402.0 K
0
0 20 40 60 80 100
p (MPa)

Figure 3.8 Variation of the solubility of adamantane in supercritical CO2 .

The data shows the variation in the pressure range from ∼10 to ∼90 MPa
and between temperatures of 343, 362, 382, and 402 K (these values
correspond to p/ pcrit = 1.36–12.20 and T /Tcrit = 1.13–1.32). Data
adapted from Swaid et al. (1985) and Kraska et al. (2002).

lower compared to adamantane. The solubilities can be fitted by the

following equation:

ln x2 = a1 + a2 (T0 /T ) + a3 ln(T /T0 ) (3.6)

where T0 = 298.15 K, and ai , i = 1, 2, 3 are fitting coefficients.

 Chemical Properties 55

10-4

10-6
x2

Adamantane
Naphthalene
10-8
Diamantane
Anthracene
Phenanthrene
10-10
300 350 400 450 500
T (K)

Figure 3.9 Molar solubilities of diamondoids and polycyclic aromatic

hydrocarbons in aqueous solutions. The graph shows the variation of the
molar solubility x2 of adamantane, diamantane, and the polycyclic aromatic
hydrocarbons naphtalene (C10 H8 ), anthracene (C14 H10 ), and phenanthrene
(C14 H10 ), whose molecular structures are also indicated. The lines are the
best fits of the solubility according to Eq. 3.6. Data adapted from Karasek
et al. (2008).

Between temperatures of T = 254 and 543 K, the sublimation

pressure of the solid phase Ada(I) is (Bazyleva et al., 2011):
ln( p/kPa) = 50.9129 − 8494.5(T /K)−1 − 4.6395 ln(T /K) (3.7)

3.1.4 Biocompatibility and Toxicity

Because of their stable structure and inertness, in recent years,
nanodiamonds have attracted increasing attention for potential
applications in biotechnology and medicine.
At the time of writing of this book, to the best of our knowledge,
there were no in vitro or in vivo studies on the toxicity of
diamondoids. However, since recently, nanodiamonds have become
an attractive alternative to other nanoparticles (e.g., functionalized
56 Chemical and Physical Properties and Characterization of Diamondoids

metallic nanoparticles) for labeling and drug delivery, studies

investigating possible toxicity effects of nanodiamonds in organisms
have increased (Krueger, 2008, 2011; Krueger and Lang, 2012).
Therefore, because from a structural point of view, diamondoids
are nanodiamonds with sizes below 2 nm, one could argue that at
least for diamondoids that are of comparable size to nanodiamonds,
similarities in the behavior of organs and organisms exist.
For biotechnology applications, nanodiamondoids have become
increasingly popular as fluorescent probes and for drug carriers,
because of their exceptional stability and inertness. Moreover, there
is no known toxicity of diamondoids. The reason why in the current
understanding, diamondoids are nontoxic is that the metabolism of
people allows diamondoids to be removed.
As will be shown in Chapter 4, nanodiamonds and diamon-
doids show promise for applications in medicine and biotechnol-
ogy (Schrand et al., 2009; Wang et al., 2003). However, this brings up
the question whether nanodiamonds, especially when used for the
treatment of humans, are toxic or not (Schrand et al., 2007b). In a
study that investigated the toxicity of several carbon nanomaterials,
nanodiamond, carbon black, multiwall carbon nanotubes and single-
wall carbon nanotubes found that the biocompatibility was highest
for nanodiamonds (Schrand et al., 2007a).
Over the last few decades, several studies of diamondoids and
their effect on organisms have been conducted. So far, these studies
have been mainly realized on cells or animals. For example, the
metabolism of several diamondoids and diamondoid derivatives in
rat livers has been investigated (Hodek et al., 1988).

Applications of nanodiamonds for bioapplications: In the following,

we discuss possible applications of nanodiamonds for bioapplica-
tions. So far, with the exception of diamondoid derivatives that have
been used in pharmaceutics, there have been no investigations on
the effect of diamondoids on cells, living tissue, etc. Moreover, as
will be shown later, at present, there diamondoids are not available
in large quantities, and therefore, the discussion has to be limited
to nanodiamonds. But we hope, that in the future, that current
applications of nanodiamonds can be extended to diamondoids.
 Physical Properties 57

The accumulation of nanodiamonds (NDs) with sizes of 50 nm

has been investigated (Yuan et al., 2010). Using mouse samples, they
found that the NDs accumulated mainly in the liver, lung, and spleen,
and that the level of nanodiamonds amassed in these organs were
kept constant even after 28 days.

3.2 Physical Properties

In this section, we will discuss the main physical properties of
diamondoids. Specifically, we will discuss the electronic structure
and how it changes when the size of the diamond increases. We
also will present some approaches for tuning the bandgap in
diamondoids, by the inclusion of atoms inside their cages, or by
functionalization. Different spectroscopic methods can be used to
characterize diamondoids and we present the main characteristics
of vibrational spectra acquired on diamondoids and their main
features. Finally, we also briefly discuss the main characteristics of
mass spectra acquired on diamondoids.
Diamondoids can assemble to larger, macroscale crystals,
bonded by weak van der Waals forces, forming structures that
resemble macroscale diamonds. However, it is at the intramolecular
sp3 carbon framework level, not the intermolecular level, that
diamond-like properties, for example, strength, rigidity, and stability,
emerge (Dahl et al., 2003a).

3.2.1 Electronic Properties

In this section, we take a closer look at how the diamondoid
structure—size, the substitution of carbon atoms in the carbon
framework, by attaching functional groups, the positions where func-
tional groups are attached—influences their electronic properties.
We also draw comparisons between the electronic structures of
diamondoids, nanodiamonds, and bulk diamond.
To assess the band structure of diamondoids, a lot of work
has been done using density functional theory (DFT), and we will
compare these works to available experimental data whenever
possible.
58 Chemical and Physical Properties and Characterization of Diamondoids

3.2.1.1 The band structure of diamondoids

In order to understand the band structure of diamondoids, we
will briefly compare them to the band structure of bulk diamond.
Figure 3.10a shows the band structure of crystalline adamantane,
diamantane, and triamantane.
The experimental bandgap of diamond is E gap ≈ 5.46–5.5 eV
and it is an indirect semiconductor.
To measure the bandgaps in diamondoids, essentially two
techniques have been employed up to now: X-ray absorption

a b
6

4
kz
E – EVBM (eV)

R Z
Γ A k
X M
y
kx
2

–2
Γ X M Γ Z R A Z 0 10 20
DOS
(states/eV/f.u.)

Figure 3.10 Electronic band structures of crystalline adamantane. (a) Band

structure of crystalline adamantane along the high symmetrical momentum
points. The inset shows the Brillouin zone for the tetragonal primitive cell
with symmetry points labeled according to the standard notation. (b) The
density of electronic states (DOS) in crystalline adamantane. The energy is
plotted with respect to the valence band maximum (E VMB ). Data adapted
from Sasagawa and Shen (2008).
 Physical Properties 59

spectroscopy (XAS) and soft X-ray emission (SXE) spectroscopy. XAS

of carbon 1s levels can be used to assess the unoccupied states
and can be used to estimate the relative energy position of the
lowest unoccupied orbitals. In contrast, SXE allows measuring
the highest occupied sp3 -hybridized states in diamondoids. In SXE,
the lower energies and their measurements suggest an increase
in the bandgap for decreasing diamondoid size. To estimate the
HOMO-LUMO gap, DFT simulations have been conducted at different
levels of theory. However, in some cases, the differences between the
various adopted methods were quite large.

Molecule

LUMO

∆E = 7.5 eV

HOMO

Figure 3.11 Orbitals of molecular and crystalline adamantane: HOMO

(bottom) and LUMO (top) of adamantane.
60 Chemical and Physical Properties and Characterization of Diamondoids

a b c d
8

6
E – EVBM (eV)

0
-1
X Γ R X Γ R X Γ S X Γ L

Diamondoids Bulk diamond

Figure 3.12 Comparison of bandgaps of crystalline diamondoids and bulk

diamond. (a) Adamantane, (b) diamantane, (c) triamantane, and (d) bulk
diamond. The energy dispersion relationship is shown around the origin
of the momentum space ( point) for the crystalline structures of the
respective diamondoids. Data adapted from Sasagawa and Shen (2008).

3.2.1.2 Effect of diamondoid size on bandgap

It has been shown that the bandgap of diamondoids can be tuned by
changing their size or by the incorporation of different particles in
the interior.
Figure 3.11 shows again an example of the HOMO and LUMO of
adamantane. Compared to the isolated molecule, in the case of solid
adamantane, the HOMOs are mainly situated around the C–C and C–
H bonds.
Figure 3.12 displays the change of the band structure between
the lower diamondoids adamantane, diamantane, and triamantane
in comparison with the one of bulk diamond. The lower diamon-
doids possess a direct bandgap (indicated by the line at the point),
whereas in bulk diamond, the bandgap is indirect.
 Physical Properties 61

Adamantane
Total ion yield absorption (step height, offset)

8
Diamantane
7

Triamantane
6
[121] Tetramantane
5
[123] Tetramantane
4
[1(2,3)4] Pentamantane
3
Hexamantane
2

1 Diamond
(× 0.5)

0
285 290 295 300 305 310 315
Photon energy (eV)

Figure 3.13 X-ray absorption spectroscopy of diamondoids in comparison

to diamond. For the sake of a better comparison, the intensities of the curve
of diamond have been multiplied by a factor of 0.5. Data adapted from Willey
et al. (2005).

The X-ray absorption spectra of various diamondoids in compar-

ison to diamond is illustrated in Fig. 3.13.
Figure 3.14 shows the variation of the normalized photo-ion
yield for diamondoids ranging from adamantane to pentamantane.
Therefore, the bandgap of diamondoids can be modified by
several approaches:

(1) Modification of the size

(2) Functionalization
(3) Inclusion of heteroatoms inside the diamondoid cage
62 Chemical and Physical Properties and Characterization of Diamondoids

Normalized photoion yield (arb. units)

Pentamantane

Tretramantane

Triamantane

Diamantane

Adamantane

Cyclohexane

7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0

Photon energy (eV)

Figure 3.14 Photo-ion yield for different diamondoids and cyclohexane.

The photo-ionization level is found by the intersection of the horizontal
line and the linear fit to the increase of the photo-ion yield. Ada:
adamantane; Dia: diamantane; Tria: triamantane; Tetra: [121]tetramantane;
Penta: [1234]pentamantane. Data adapted from Lenzke et al. (2007).

The variation of the bandgap of diamondoids as obtained simu-

lations is illustrated in Fig. 3.15, which shows the variation of
the bandgap for both icosahedral and octahedral diamondoids. By
increasing the size from adamantane (C10 H16 , n = 1 ) to C286 H144
the bandgap decreases from about 9.5 eV to about 6.8 eV.
 Physical Properties 63

10

C10H16

C26H32 C36H36
Bandgap eV

8
C84H64
C51H52

C87H76 C165H100
7 C136H104 C281H172
C200H136
C286H144

6
Octahedral
Icosahedral

5
0.0 0.5 1.0 1.5 2.0 2.5
Diamondoid size (nm)

Figure 3.15 Variation of the bandgap of diamondoids as a function of

diamondoid size. The bandgaps, estimated from density functional theory
simulations, are shown for C10 H16 to C286 H144 , for both diamondoid clusters
with icosahedral and octahedral symmetry. Data adapted from Fokin and
Schreiner (2009).

3.2.1.3 HOMO-LUMO variation by functionalization of

diamondoids
In addition to the size of the diamondoids, the bandgap of diamon-
doids can be modified by partially replacing the H terminations by
other atoms or molecules.
Figure 3.16 to 3.18 show valence spectra of diamantane and
functionalized diamantane acquired by photoelectron spectroscopy,
which illustrate the effect of different functionalization strategies.
Figure 3.19 displays the variation of the orbital energies of sulfur-
doped diamondoids (thiamantanes).
64 Chemical and Physical Properties and Characterization of Diamondoids

hν = 21.22 eV OH

Cage structure edge IP

SH
Intensity (arb. units)

IP

NH2

IP

IP

11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5

Binding energy (eV)

Figure 3.16 Valence spectra of diamantane and functionalized diamantane.

The arrows indicated the ionization potentials (IPs), and the dashed line
indicates the approximate position of the cage structure edge. Data adapted
from Rander et al. (2013).

3.2.1.4 Variation of the HOMO-LUMO gap by the inclusion of

small atoms inside diamondoids
In addition to bandgap tuning by functionalization, that is, the
replacement of the hydrogen termination by functional groups,
another possibility that has been investigated by Marsusi et al.
(Marsusi and Mirabbaszadeh, 2009) is by including different small
atoms (Li, Be, He, and Ne) at the interior of the diamond cage.
Figure 3.20 shows the molecular structures of the first three
diamondoids and an included atom.
 Physical Properties 65

hν = 21.22 eV IP trend
SH
IP

SH
Intensity (arb. units)

SH
IP

SH
IP

IP SH

10.0 9.5 9.0 8.5 8.0

Binding energy (eV)

Figure 3.17 Valence spectra of diamondoid thiols. The arrows indicated

the ionization potentials (IPs), and the dashed line indicates its trend. Data
adapted from Rander et al. (2013).

Figure 3.21 shows the variation of the HOMO-LUMO gaps

calculated for different structures similar to those shown in Fig. 3.20.
Specifically for adamantane, the effect of encapsulating transition
metal atoms inside its cage has been investigated in detail (Garcia
et al., 2011).
In addition the influence of a single thiol group on the electronic
and optical properties of the smallest diamondoid adamantane has
also been investigated (Landt et al., 2010).
66 Chemical and Physical Properties and Characterization of Diamondoids

hν = 21.22 eV
[121]tetramantane-2-thiol

SH SH

[121]tetramantane-6-thiol
Intensity (arb. units)

Triamantane-3-thiol
SH

SH
Triamantane-9-thiol
Diamantane-4-thiol
SH Diamantane-1-thiol

SH

9.5 9 8.5 8
Binding energy (eV)

Figure 3.18 Variation of valence spectra of diamondoid thiols as a

function of position. The curves show the spectra for the thiol derivates
of diamantane, triamantane, and [121]tetramantane, for both apical and
median positions. Data adapted from Rander et al. (2013).

0.1 LUMO+2

LUMO+1
LUMO
Orbital energy atomic units

0.0
S
S
S

0.1 S

HOMO
0.2
   HOMO-1


HOMO-2

0.3

0 5 10 15 20
Number of cages in thiamantane n

Figure 3.19 Variation in the orbital energies of the unoccupied and occu-
pied states with increasing size of S-doped diamondoids (thiamantanes).
The calculations were conducted at the B3PW91/6-31G(d, p) level of theory.
Data adapted from Fokin and Schreiner (2009).
 Physical Properties 67

a b c

X@C10H16 X@C18H24 X@C26H32

Figure 3.20 Schematic of molecular structures with atoms included inside

diamondoid cages. (a) Adamantane, (b) triamantane, and (c) [1(2,3)4]pen-
tamantane. The atom inserted inside the cage (noted X) investigated were
Li, Be, He, and Ne. For clarity, the atoms are not drawn to scale and for
X@triamantane and X@[1(2,3)4]pentamantane, the hydrogen atoms are
not shown.



Relative HOMOLUMO gap eV

2  
  

 


 
0   
 

2
 X Adamantane
4  X Diamantane 
 X Triamantane
 X Si10H16

6 
Li(+) Be Be(2+) Na(+) Mg(2+) He Ne F(-)

Figure 3.21 Relative HOMO-LUMO gaps of doped diamondoids consisting

of different inclusion atoms calculated at the B3LYP/6-31G(d,p) level
of theory. These structures represent possible spin singlet complexes
X@C10 H16 , X@C18 H24 , and X@C26 H32 . The data is shown relative to the
corresponding single-cage gaps, along with the relative HOMO-LUMO gap
of Si10 H16 taken from Pichierri (2006). Data adapted from Marsusi and
Mirabbaszadeh (2009).
68 Chemical and Physical Properties and Characterization of Diamondoids

3.3 Optical Properties

3.3.1 Vibrational Spectroscopy of Diamondoids
3.3.1.1 Infrared spectroscopy
The vibrational spectra of adamantanes have been investigated
in detail by Ramachandran et al. (Ramachandran and Manogaran,
2006, 2007), while the infrared spectrum of the adamantyl cation
has been examined by Polfer et al. (2004).
A systematic study of infrared spectra on different diamon-
doids—adamantane, diamantane, triamantane, [121]tetramantane,
[1(2,3)4]pentamantane, and [12312]hexamantane—was conducted
by Pirali et al. (2007). In addition to experimental measurements
and owing to more performant computing power, in recent years
the details of the vibrational spectra were also investigated via
numerical simulations (Banerjee and Saalfrank, 2014).
Figure 3.22 displays experimentally acquired spectra of various
diamondoids ranging from adamantane to [12312]hexamantane.
As can be seen from the graphs in Fig. 3.22, the number of
spectral features depends on the symmetry of the diamondoid
investigated. Higher symmetry leads to less peaks.
In the case of enantiomers, unless a polarized light source is used,
there is no difference in the spectra.

3.3.1.2 Raman spectroscopy of diamondoids

Before discussing the main characteristics of Raman spectra of
diamondoids in detail, we briefly give an overview of Raman
spectra of other carbon nanomaterials, that is, such that are sp1 ,
sp2 , or sp3 hybridized. Figure 3.23 displays the Raman spectra of
diamond, graphite, the fullerene C60, carbon nanotubes (CNTs), and
adamantane.
A first detailed study of the vibrational modes of admantane
has been conducted by R. T. Bailey (Bailey, 1971), and later studies
on the lower diamondoids up to triamantane also investigated
the effect of temperature on the vibrational features (Jenkins and
Lewis, 1980). As has been mentioned in Section 3.1.1, the lower
 Optical Properties 69

Adamantane

Diamantane
Intensity arb. unit

Triamantane

[121]Tetramantane

[123]Tetramantane

600 800 1000 1200 1400 1600 2800 2850 2900 2950 3000
Wavenumber (cm-1)

Figure 3.22 Attenuated total reflection Fourier transform infrared (ATR-

FTIR) spectra of diamondoids. The data is the one of adamantane
(adapted from Garcia et al., 2010c), diamantane, triamantane, and [121]-
and [123]tetramantane (data adapted from Oomens et al., 2006). The
light source for acquiring the spectra was not polarized; therefore the
spectra of [123](P) and (M) tetramantane are the same. The spectrum for
tetramantane corresponds to a racemic mixture of the (P) and (M) forms
(i.e., equal proportions of the right [dextro-] and left-rotatory [levo-] forms).

diamondoids—adamantane, diamantane, and triamantane—exhibit

a transition to a premelting plastic phase. In the case of adamantane,
this transition occurs at 209 K, at 447 K for diamantane and at
T > 428 K for triamantane.
In the following, we briefly discuss the different spectral features
of adamantane in more detail. Since adamantane consists of
24 atoms, it has 3N − 6 = 72 vibrational modes ( vib )mol ,
( vib )mol = 5A 1 + A 2 + 6E + 6T1 + 10T2 (3.8)
with A i symmetric modes.
As already mentioned, because of the complexity of Raman
spectra of diamondoids, numerical simulations can help to interpret
such spectra. One example was the theoretical confirmation of
70 Chemical and Physical Properties and Characterization of Diamondoids

1332

Diamond
1582

Graphite
2000
42

1350
Intensity arb. unit

Carbyne

1460

C60
493 1425 1573

1581
CNT
186 1567

1331

756 1222
Adamantane

972 1434
1097

0 500 1000 1500 2000

Raman shift (cm-1)

Figure 3.23 Raman spectra of various carbon materials. The data is

representative of different carbon materials and hybridizations: diamond
(sp3 ), graphite (sp2 ), carbyne (sp1 ), the fullerene C60 (sp2 ), carbon
nanotubes (CNTs, sp2 ), and the first diamondoid, adamantane (sp3 ).

the experimental Raman spectra of cyclohexamantane (Richardson

et al., 2005).
For nonlinear molecules with N atoms, the total number of
normal vibrational modes (i.e., modes that are relatively simple such
as stretching mode) is 3N −6 while for linear molecules, it is 3N −5).
Diamondoid molecules contain specific vibrational modes that
can be probed by Raman spectroscopy.
Such symmetry considerations allow to determine the number
of theoretically Raman active vibrational modes. Detailed character-
 Optical Properties 71

CCC bend / CC stretch CH wag / twist CH2 scissor CHx (sp3) (sp2) stretch

Adamantane
Intensity arb. unit

Diamantane

Triamantane

200 400 600 800 1000 1200 1400 1600 2800 2850 2900 2950 3000
Raman shift (cm-1)

Figure 3.24 Experimental Raman spectra of the lower diamondoids

adamantane, diamantane, and triamantane. For easier presentation, the
high-frequency domain and the low-frequency domains have been sepa-
rated. Data adapted from Filik et al. (2006a).

ization of diamondoids using different Raman wavelengths has been

conducted by (Filik et al., 2006a).
A series of characteristic Raman spectra of lower diamondoids
are shown in Fig. 3.24.
The arrows in the molecule indicate the vibrational modes of the
diamondoids.
As in the infrared spectra, Raman spectra of diamondoids can
be divided into several regions that are characteristic of certain
vibrational modes of the diamondoids.
In addition to the experimental Raman spectra shown in
Figs. 3.24–3.28, attempts have been undertaken to simulate these
spectra numerically (Filik et al., 2006a,b). In addition, the Raman
spectra of cyclohexamantane have been investigated using density
functional theory (Richardson et al., 2006).
With increasing cage number n, the vibrational features in both
the Raman and infrared spectra become more and more complex.
Therefore, to assign the peaks in the experimentally acquired
spectra, ab initio simulations have been performed in parallel.
72 Chemical and Physical Properties and Characterization of Diamondoids

CCC bend / CC stretch CH wag / twist CH2 scissor CHx (sp3) (sp2) stretch

[121]
Intensity arb. unit

[123]

[1(2)3]

200 400 600 800 1000 1200 1400 1600 2800 2850 2900 2950 3000
Raman shift (cm-1)

Figure 3.25 Experimental Raman spectra of [121], [123], and [1(2)3]tetra-

mantane. The spectra in the region of 200–1800 cm−1 have been normalized
with respect to the peak intensity at ∼1200 cm−1 . Data adapted from Filik
et al. (2006a).

CCC bend / CC stretch CH wag / twist CH2 scissor CHx (sp3) (sp2) stretch

[1212]pentamantane
Intensity arb. unit

[1213]pentamantane

[1234]pentamantane

200 400 600 800 1000 1200 1400 1600 2800 2850 2900 2950 3000
Raman shift (cm-1)

Figure 3.26 Experimental Raman spectra of [1212], [1213], and [1234]

pentamantane. The spectra in the region of 200–1800 cm−1 have been
normalized with respect to the peak intensity at ∼1200 cm−1 . Data adapted
from Filik et al. (2006a).
 Optical Properties 73

CCC bend / CC stretch CH wag / twist CH2 scissor CHx (sp3) (sp2) stretch

[12(3)4]pentamantane
Intensity arb. unit

[12(1)3]pentamantane

[1(2,3)4]pentamantane

200 400 600 800 1000 1200 1400 1600 2800 2850 2900 2950 3000
Raman shift (cm-1)

Figure 3.27 Experimental Raman spectra of [12(3)4], [12(1)3], and

[1(2,3)4]pentamantane. The spectra in the region of 200–1800 cm−1 have
been normalized with respect to the peak intensity at ∼1200 cm−1 . Data
adapted from Filik et al. (2006a).

CCC bend / CC stretch CH wag / twist CH2 scissor CHx (sp3) (sp2) stretch
Intensity arb. unit

[121321]heptamantane

200 400 600 800 1000 1200 1400 1600 2800 2850 2900 2950 3000
Raman shift (cm-1)

Figure 3.28 Experimental Raman spectra of [121321]heptamantane. The

spectra in the region of 200–1800 cm−1 have been normalized with respect
to the peak intensity at ∼1200 cm−1 . Data adapted from Filik et al. (2006a).
74 Chemical and Physical Properties and Characterization of Diamondoids

a Raman inactive
Raman inactive Raman inactive Eg
BLM mode Eu modes
mode A2u A1g Eu A2u A
1g
Intensity (arb. units)

OH

SH

NH2

Raman shift (cm-1)

b Raman inactive BLM Raman inactive Eg Raman inactive

mode A2u A1g mode Eu Eu modes A A
2u 1g

Intensity (arb. units)

Intensity (arb. units)

Raman shift (cm-1) Raman shift (cm-1)

Figure 3.29 Experimental Raman spectra of functionalized diamantane.

Data adapted from Meinke et al. (2013).

In the last part of this section, we will have a look at the effect of
the functionalization on the modification of Raman spectra.
However, while such Raman spectra allow to understand the
modifications, currently it is still not possible to simulate the
experimental spectra with 100% accuracy. One of the reasons is that
the ab initio simulations of Raman spectra involved the calculation
of the derivative of the polarization tensor, which is computationally
time consuming.
In addition, in the simulations, only isolated molecules are
considered, whereas in real Raman spectra, the nature of the
crystal lattice leads to additional peaks and shifts. Table 3.2 lists
vibrational modes of adamantane ([0]), diamantane ([1]), and select
triamantanes and pentamantanes.
Raman scattering experiments of triamantane in the low fre-
quency range (∼0–100 cm−1 ) for temperatures between 40 and
Table 3.2 Summary of known vibrational modes of diamondoids. We list again the symmetry of the molecules. Vibrational
modes that are not Raman active are marked with the superscriptna , and degenerative modes withg . Data adapted from
Filik et al. (2006a)

Vibrational modes
Raman
Diamondoids Symmetry Total A1 A2 A1g A1u A2g A2u B1 B2 Bg Bu E Eg Eu T 1 T2 active
[0] 72 5na 1 6 7na 11 22
na na na na
[1] 96 11 6 5 10 16 16 27
[12] C 2ν 120 35 25 29 31 120
[121] [1(2)3] C 3ν 144 29 19na 48d 77
[1212]
[1(2, 3)4] Td 168 10 4na 14 18na 24 48
Optical Properties
75
76 Chemical and Physical Properties and Characterization of Diamondoids

340 K showed a phase transition at about 285 K (Jenkins, 1978).

This phase transition was found to be consistent with previous XRD
measurements and are due the change from an ordered structure
24
(D2h , Z = 16) to a disordered structure (D2h
25
, Z = 2).
Recently, the effect of pressure on Raman and XRD spectra in
[121]tetramantane has also been investigated (Yang et al., 2014).
Functionalizing diamondoids leads also to changes in both their
infrared and Raman spectra. For example, both Raman and infrared
spectra of functionalized diamondoids have been analyzed both
experimentally and theoretically using density functional theory
analysis (Bistricic et al., 2002), see Fig. 3.30, which shows the

a
Intensity arb. unit

Adamantane

Adamantanone

400 600 800 1000 1200 1400 1600

Wavenumber (cm–1)

b
Intensity (arb.unit)

Adamantane

Adamantanone

400 600 800 1000 1200 1400 1600

Raman shift (cm–1)

Figure 3.30 Infrared and Raman spectra of adamantane and adaman-

tanone. (a) Infrared spectra of adamantane and adamantanone. (b) Raman
spectra of adamantane and adamantanone. Data adapted from Bistricic et al.
(2002).
 Mass Spectrometry of Diamondoids 77

experimental infrared and Raman spectra of adamantane and

adamantanone.
In short, vibrational spectroscopy can be used for “finger-
printing” diamondoids. However, for this, it is necessary to have
sufficiently quantities of purified material at hand, typically on the
order of milligrams, otherwise it is not possible to conduct the
spectroscopy measurements.

3.4 Mass Spectrometry of Diamondoids

While vibrational spectroscopy methods are relatively easy to
conduct, the requisite is that one has a purified sample, preferably
in crystalline form. In addition, these methods are only applicable if
the products are available in at least milligram quantities.
As will be discussed in later chapters, with the exception of lower
diamondoids and higher diamondoids extracted and isolated from
oil and gas reservoirs, they are not available in large quantities.
Another method that allows analyzing products is gas
chromatography–mass spectrometry (GC-MS), which enables the
detection of samples of very small quantities.
In this section, we will give an overview of mass spectra of
diamondoids and their main features.
The mass spectra contain usually a prominent molecular ion
peak, that is attributed to the molecular ion (denoted M+• ). Since
diamondoids are closed-shell molecules, singly ionized molecules
are odd-electron ions (i.e., open shell). In addition, depending on
the ionization energy, the mass spectra often contain a peak at M/2,
which is due to the double ionized molecule, M2+ .
Figure 3.31 displays the mass spectra of adamantane and
diamantane, the data being used from the NIST Mass Spectral
Library (NIST/EPA/NIH Mass Spectral Library (EI), 2012).

3.4.1 Nuclear Magnetic Resonance Spectroscopy of

Diamondoids
While vibrational spectrosocopy is the method of choice for char-
acterizing diamondoids, to obtain meaningful data, it is necessary
78 Chemical and Physical Properties and Characterization of Diamondoids

a 100
Adamantane M+•
136
80
Relative intensity (%)

60

40

20

0
0 20 40 60 80 100 120 140
mz

b 100
M+•
Diamantane
188
80
Relative intensity (%)

60

40
91
79 131
20 105 117
67 145 159
53
173
0
50 100 150 200
m/z

Figure 3.31 Mass spectra of adamantane and diamantane. (a) Adamantane

and (b) diamantane. The peaks at m/z 136 and 188 are attributed to the
respective molecular ions M+• of adamantane and diamantane, while the
others correspond to fragment ions. The peaks at M/2 are due to the doubly
ionized molecule M2+ .

to have sufficient quantities of diamondoids (typically on the order

of milligrams). As has been shown in the previous sections, the
vibrational spectra of especially the lower diamondoids are well
known and with the aid of computational simulations, also allow to
assign peaks of higher diamondoids (Filik et al., 2006a). However,
in cases where the exact substance is not known, it is necessary to
resolve to other techniques.
 Mass Spectrometry of Diamondoids 79

13
Table 3.3 C chemical shifts for adamantane and diamantane

Name Molecular formula Dualist code Crystal structure

Adamantane C10 H16 [0] Fm3m (Oh )

Diamantane C14 H20 [1] Pa3 (Th6 )

While not as widely employed as vibrational spectroscopy

methods, nuclear magnetic resonance (NMR) techniques have also
been used to characterize diamondoids, but so far, they include
mainly the smallest diamondoids, that is, adamantane, diamantane,
and certain derivatives (Hajek et al., 1985; Horska et al., 1988). One
exception is the work of Panich et al. (2006), who investigated NMR
spectra of ultrananocrystalline diamonds.
Table 3.3 lists the 13C chemical shifts of adamantane and
diamantane.
Chapter 4

Current and Future Applications of

Diamondoids and Their Derivatives

In this chapter, we will briefly present a few of the current and

possible future applications of diamondoids and their derivatives.
Because of their advantageous properties, especially with respect to
thermal and chemical stability, they hold promise for a wide range
of possible applications. The first part of this chapter focusses on
diamondoids used as probes in oil and gas reservoir exploration,
while the second treats current advances in the use of diamondoids
in chemistry, pharmaceutics, medicine, and biotechnology. The third
part presents examples of the use of diamondoids in materials
science and nanotechnology, while the last part gives a brief outlook
on possible future applications.

4.1 Overview
In recent years, diamondoids have elicited increasingly interest
as possible nanomaterials. Work by several groups has suggested
that their special properties—high thermal stability, well-defined
structure, and no known toxicity—makes them interesting for

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
82 Current and Future Applications of Diamondoids and Their Derivatives

applications for a wide range of applications (Freitas and Merkle,

2008).
These possible applications of diamondoids include pharmaceu-
tics and chemistry, biotechnology, and nano- and optoelectronics.
However, to date, one of the most common applications of
diamondoids is as markers for the evaluation of the maturity of
petroleum and gas fields.
In the following sections, we will briefly present these applica-
tions more in detail, together with relevant works from the literature.
We have divided these different applications into different fields,
but these have been chosen more or less arbitrarily. At the time
of writing of this book, we tried to include the latest research on
diamondoids; however, since this is still a work in progress, new
applications are certain to be found.

4.2 Applications of Diamondoids in Oil

Exploration
Owing to their high thermal stability compared to alkanes of similar
molecular weight, diamondoids persist in petroleum reservoirs,
leading to a gradual increase in their concentration during crack-
ing (Dahl et al., 1999). This diamondoid concentration can be used
to identify the possible occurrence and extent of oil destruction, and
the oil deadline in a particular basin. The oil deadline describes
the conditions where oil can be formed: typically at depths of
5 km and temperatures of 150◦ C–175◦ C (recent experiments show
that petroleum can persist at temperatures higher than 200◦ C).
Otherwise, there is onset of oil cracking, that is, formation of gas and
pyrobitumen.
Because of their high thermal stability, diamondoids find appli-
cation in characterizing natural gas condensates and gasoline (Stout
and Douglas, 2004). Another important application of diamondoids
is in environmental fingerprinting and environmental forensics. The
relative abundance of different diamondoids or their derivatives,
especially those of adamantane and diamantane, and the high heat
resistance can be used. Consequently, diamondoids have been used
 Applications of Diamondoids in Oil Exploration 83

to characterize oil and gas reservoirs in many different locations.

For example, diamondoids were used to assess the maturity of
gas condensates in the Southern Indus Basin (Pakistan) (Nasir and
Fazeelat, 2013). Moreover, the presence of diamondoids allows for
identifying the source in oil spills (Lengger et al., 2013; Mansuy et al.,
1997).

4.2.1 Formation of Diamondoids in Natural Gas

Reservoirs
Diamondoids found in petroleum sources result from carbocation
rearrangements of organic precursors, for example multiringed
terpene hydrocarbons deposited on clay mineral superacids. It has
been suggested that during oil cracking, they are neither formed
nor destroyed but conserved and their increased concentration
can be used for estimating the extent of conversion of liquid
to gas and pyrobitumen. The formation of lower diamondoids is
mainly attributed to (1) Lewis acid–catalyzed rearrangements of
polycyclic hydrocarbons (Lin and Wilk, 1995; Wingert, 1992); (2)
high-temperature cracking of high-molecular-mass fractions (Giruts
et al., 2006; Giruts and Gordadze, 2007).
Figure 4.1a illustrates the principle of a Lewis acid and base:
A Lewis base provides two electrons, whereas a Lewis acid is
an electron pair acceptor. The reaction in Fig. 4.1b shows the

a Electron b AlBr3, t-BuBr

Vacant
Filled orbital 50-60 ºC, 1 h
orbital

B + A
65%
Lewis base Lewis acid

B A

Figure 4.1 Example of Lewis acid catalyst. (a) Lewis acid: acceptor of
two electrons. (b) Example of a Lewis acid–catalyzed rearrangement
of a polycyclic hydrocarbon: formation of 3,5-dimethyladamantane from
perhydrogenated phenanthrene in AlBr3 (aluminum bromide) and t-BuBr
(tert-butyl bromide).
84 Current and Future Applications of Diamondoids and Their Derivatives

a
Natural Crude oil
gas

Asphaltene
Methane

Carbon
Hydrogen
Sulfur
Oxygen
Nitrogen Tar

Gas
Oil

Figure 4.2 Overview of possible natural sources for the formation of lower
diamondoids. (a) Natural gas and crude oil. (b) Oil reservoir.

catalyzed rearrangement of a polycyclic hydrocarbon, perhydro-

genated phenanthrene, to 3,5-dimethyladamantane in aluminum
bromide.
Laboratory experiments have shown that lower diamondoids
(i.e., n ≤ 4) can be obtained from different natural sources:
sedimentary rocks, peats, kerogens, and crude oil and their different
group components (i.e., saturated and polar fractions [resin and
asphaltene]) and, finally, carbon compounds (C16 , C19 , C22 , C34 , C36 ,
and n-alkanes).
Figure 4.2 gives an overview of different natural sources of
diamondoids.
Despite their high thermal stability—especially when compared
to other carbon materials such as alkanes, etc.—studies have shown
 Applications of Diamondoids in Oil Exploration 85

that lower diamondoids can be destroyed at temperatures that are

higher than those during their generation (Fang et al., 2012; Wei
et al., 2006), that is, at temperatures above T = 340◦ C.
At higher maturation levels, C3 - and C4 -alkylated adamantanes
are probably more stable than other adamantanes.
The formation of lower diamondoids in petroleum consists of
three main stages: (1) early generation during the formation of
oil (∼0.8–1.0% EasyRo), (2) generation during the cracking of oil
(>1% EasyRo), and (3) destruction of diamondoids during the late
stages of oil cracking (2% EasyRo).
The most abundant adamantane and diamantane sources are
saturated oil fractions in the maturity range of 1.0%–2.3% for
adamantane and 1.6%–2.5% for diamantane. The second-most
abundant source of adamantanes and diamantanes is resin and
aromatic fractions. In contrast, the contents of diamondoids in the
asphaltene fraction was almost negligible. Finally, in the evolution
curve of diamondoids, rapid destruction is observed.
The origins and formation mechanisms of diamondoids in oils
and source rocks are still a matter of debate and many studies being
conducted in order to understand the conditions (i.e., temperatures
and pressures, but also the type of rocks and sediments) that can
lead to the formation of diamondoids (Fang et al., 2013, 2012).
Diamondoids are absent in recent organic matter; therefore
they are probably not of biosynthetic origin, that is, formed within
living organisms (bacteria, etc.) or cells. Currently, diamondoids
are thought to be formed during diagenesis (i.e., the formation
of sediments to sedimentary rocks) and the catagenesis (i.e., the
cracking process during which organic kerogens are converted into
hydrocarbons) of organic matter. Kerogen is a collective name for
an organic material that is insoluble in organic solvents, water, or
oxidizing agents. Kerogen consists of very large molecules (and
could be considered a polymer). When exposed for sufficiently long
times and high temperatures, kerogens again crack down to smaller
molecules, mostly petroleum.
In addition to natural oil and gas reservoirs, diamondoids,
nanodiamonds, and diamondoids have also been observed in
space (Lewis et al., 1987).
86 Current and Future Applications of Diamondoids and Their Derivatives

4.3 Current and Possible Future Applications of

Diamondoids and Derivatives in Chemistry,
Pharmaceutics, Medicine, and Biotechnology
4.3.1 Applications in Chemistry
4.3.1.1 Host–guest chemistry
Host–guest chemistry involves binding of a guest molecule by a
host molecule, the bond between the molecules being noncovalent.
Noncovalent bonds can involve hydrogen bonds, ionic bonds,
van der Waals forces, or hydrophobic interactions. Examples of
diamondoids acting as hosts in host–guest chemistry are given
in (Voskuhl et al., 2012). In this specific work, diamondoids
are included inside sugar rings. There are other possible guest
molecules, for example, cyclodextrins, calixarenes, pillararenes,
cucurbiturils, porphyrins, metallacrowns, crown ethers, zeolites,
cyclotriveratrylenes, cryptophanes, carcerands, and foldamers. One
example of a host molecule that is obtained by substitution by
1-adamantyl is calix[4]arene.
Diamondoids—specifically adamantane—have also been used as
a seed for diamond film growth (Tiwari et al., 2010, 2011).
Figure 4.3 gives an example of a host–guest chemistry based on
adamantane. In this particular case, methyladamantane units are
attached to cyclodextrin.

4.3.2 Applications of Diamondoids in Pharmaceutics and

Medicine
Polycyclic cage compounds (Marchand, 1995), to which diamon-
doids belong, have important pharmaceutical applications: They
have shown potential for the treatment of neurodegenerative
diseases such as Parkinson’s and Alzheimer’s diseases, and they
also possess activity against virus infections such as influenza virus
A, human immunodeficiency virus (HIV), and others. The potential
of diamondoids as anti-Parkinson’s agents was suggested already
in the 1970s (Chakrabarti et al., 1976). The chemical stability and
well-defined cage structure of diamondoids are the reason that they
 Possible Applications in Chemistry, Pharmaceutics, Medicine, and Biotechnology 87

S S
OH
R OH HO R
OH

S S R=

Figure 4.3 Illustration of host–guest chemistry based on adamantane. The

methyladamantane units, indicated by R in the cyclodextrin molecule, are
attached to the aromatic rings in the structure.

can act as useful scaffolds for the attachment of side chains, which
permits the synthesis of drugs. In the following section, we will
discuss the properties of the most commonly used adamantane
derivatives that so far have been used for the treatment of various
diseases.
The first adamantane derivative that was discovered to show
promise for pharmaceutical applications was adamantane amine
(IUPAC name 1-amino-adamantane) (see Fig. 4.4), also commonly
named amantadine, which showed activity against different viruses
(influenza, hepatitis C, and herpes zoster neuralgia). Amantadine
has been found to inhibit the decapsidation stage of influenza virii,

N N N

Amantadine Memantine Rimantadine

Figure 4.4 Molecular structures of the currently most commonly used

adamantane derivatives in pharmaceutics: amantadine, memantine, and
rimantadine.
88 Current and Future Applications of Diamondoids and Their Derivatives

that is, the removal of the protein shell (capsid) that encloses the
genetic material of a virus, thereby obstructing its reproduction.
Another function amantadine is believed to perform is to effectively
block ion channels for virus entry, by forming hydrogen bonds with
a histidine residue (His-37), in the M2 transmembrane domain
protein of the influenza virus.
Rimantadine (alpha-methyl-1-adamantane-methylamine hydro-
chloride) is another adamantane derivative, in addition to amanta-
dine and memantine (see Fig. 4.4). Amantadine (1-adamantanemine
hydrochloride) and memantine (displayed in the middle of Fig. 4.4)
both show anti-Parkinsonian activity. In the following paragraphs,
we treat the case of rimantadine. In 1993, rimantadine, which is
the alpha-methyl derivative of amantadine, was approved by the US
Food and Drug Administration for the prophylaxis and treatment
of influenza A virus (although later studies suggest that the
activity against influenza A decreased). Compared to amantadine,
rimantadine has a few advantageous properties:

(1) It has fewer central nervous and sleep side effects.

(2) Its elimination half-life, that is, the time it takes the body to
reduce its quantity by half, is about 24 to 36 hours, compared
to 12–18 hours for amantadine.
(3) It possesses a 10 times higher partition coefficient when
compared to amantadine.

With regard to the first point, a study on 251 healthy adults

(Evidente et al., 1999) showed that daily doses of 300 mg.day−1 of
amantadine lead to significant central nervous system side effects.
These included nervousness, lightheadedness, and concentration
troubles. The subjects were also four times more likely to experience
sleep disturbance, namely insomnia or fatigue.
Concerning the second point mentioned above, a longer half-life
means that a single daily dose is sufficient for treatment. And a
higher partition coefficient, which expresses the ratio of equilibrium
drug concentration in lipids or fatty acids to that in water, leads to
larger intracellular concentrations and faster transport across the
blood–brain barrier of rimantadine. Studies conducted using animal
 Possible Applications in Chemistry, Pharmaceutics, Medicine, and Biotechnology 89

models showed that rimantadine enters the brain 10 times more

rapidly than amantadine.
In the treatment of Parkinson’s disease patients, about 80% of
patients reported a self-perceived improvement (Evidente et al.,
1999). However, there are also a few disadvantages related to the use
of rimantadine. The first is that it loses its effect against Parkinson’s
disease after several months, similar to amantadine. In addition, for
some patients, it can lead to other side effects.
The exact molecular mechanism of how rimantadine leads to
an improvement in Parkinson’s disease patients is still not entirely
clear. Studies suggest that its possible mechanisms are similar to
that of amantadine, whose anti-Parkinson’s effects include increased
synthesis, release, or diminished reuptake of dopamine, a neuro-
transmitter whose quantity is diminished in Parkinson patients,
reducing their motor ability. Furthermore, amantadine also leads
to anticholinergic effects, that is, it inhibits the physiological action
of acetylcholine, a neurotransmitter, thereby blocking involuntary
muscle movements caused by diseases such as asthma, incontinence,
gastrointestinal cramps, and muscle cramps.
Alzheimer’s disease has become one of the most common
diseases of aged populations, especially in industrialized countries.
Estimates of affected people are in the range of 15 million
people, and the number is constantly rising (Reisberg et al.,
2003). Alzheimer’s disease results in reduced cognitive and motor
capacities in affected persons and in moderate-to-severe stages
impairs significantly not only mental capabilities but also instru-
mental and daily basic activities. While there are pharmaceutical
drugs for treating mild-to-moderate Alzheimer’s disease, currently
there are no treatments for advanced stages. One reason for the
reduced cognitive capabilities as Alzheimer’s disease progresses is
the overstimulation of a specific receptor, N-methlyl-D-aspartate
(NMDA), by glutamate, one of the main neurotransmitters in the
brain. In addition to Alzheimer’s disease the NMDA receptor is
also implicated in other brain-related diseases, reduced memory
capabilities, and dementia. A 28-week study in 252 moderate-to-
severe Alzheimer patients aged at least 50 years old and more
than 75 years on average showed significant reduced degeneration
on different impairment scores when being administered daily
90 Current and Future Applications of Diamondoids and Their Derivatives

doses of 20 mg of memantine (1-amino-3,5-dimethyladamantane),

an adamantine derivative. That study indicated that memantine
acts as an NMDA antagonist, reducing the effect of overstimulation
by glutamate, thereby alleviating symptoms related to Alzheimer’s
disease. In 2003, memantine was approved by the Federal Drug
Administration (FDA) under the trade name Namenda R
for the
treatment of Alzheimer patients.
In addition to the three main adamantane derivatives—
amantadine, memantine, and rimantine—discussed above and
that have been found to show promise as pharmaceutical drugs,
following the discovery of the positive effects of amantadine in
treating different diseases, other adamantane derivative–based
compounds have been investigated over the years.
The first orally active antiviral drug used in the United States was
amantantadine hydrochloride. The beneficial effect of amantadine
on Parkinson’s disease was discovered accidentally when patients
were administered adamantine for treating influenza infections.
Studies indicate that one of the reasons adamantine leads to
improvement in the condition of Parkinson patients by either
increasing dopamine levels by inhibiting dopamine reuptake or
stimulating dopamine release. Furthermore, by docking to binding
sites located in receptor/ion-channel complexes, adamantine blocks
the uptake of calcium ions into neurons. Over the years, various
types of adamantane derivatives have been synthesized for use in
pharmaceutics. The advantage of using adamantane is that it can
both act as a scaffold for functional groups, especially side chains,
and, therefore, improve a drugs lipophilicity, that is, its capability
to be dissolved in lipids or fats. This means that a drug can be
transported more easily across cellular membranes, and it may
lead to easier attachment of the drug in receptors. Finally, such
adamantane-based drugs afford metabolic stability, which leads to a
prolonged effect of the drug. This means that both the drugs’ dosing
quantity and frequency can be reduced, helping to improve patients’
compatibility and compliance.
Figures 4.5 and 4.6 show the molecular structures of adaman-
tane derivatives that have been used for various pharmaceutical
applications.
 Possible Applications in Chemistry, Pharmaceutics, Medicine, and Biotechnology 91

X Anti-hyperglemic agent
X: CH3; Y: H or NH2
Y SO2HNOCHN

Anabolic steroid
OCO

O
O F

HO Chemotherapeutic agent
N O
O
H H
H H
O H

O
R1

Sedative
R2 CONH2 R1; and R2: H or CH3

R3

Anti-cataleptic
NR X: Cl or Br

Anti-cholinergic
X: OH or NH2

Figure 4.5 Molecular structures of adamantane derivatives and their

activity against specific diseases.

In summary, adamantane derivatives have shown promise for a

wide range of drugs and for treating various diseases and infections.
While currently, there are no drugs based on diamondoids other
than adamantane, it is expected that because larger diamondoids
92 Current and Future Applications of Diamondoids and Their Derivatives

NH Anti-viral (including HIV)

NH2

CNS-anti-apoptotic agent
H3C CH3

ONO2 R4 R5

–O R6 Anti-oxidant,
N+ NMDA receptor modulator
R8 R7

R3 R1

H R2
N
N
Anxiolytic and
O N N
anti-depressant

O Non-competitive Group 1
N
metabotropic glutatmate
N receptor antagonist
H
N

N Steroid sulfatase inhibitor

O O
S
NH2 O O

Figure 4.6 Molecular structures of adamantane derivatives and their

activity against specific diseases (continued).

have a similar molecular structure as adamantane, they could also

be useful for pharmaceutical applications.

4.3.3 Current and Possible Future Applications of

Diamondoids for Drug Delivery
Drug delivery is the attachment of a given drug to a carrier, called
vector, which transports the drug to the destined location in the
cell and then releases it. As already mentioned previously, one of
the attractive properties of diamondoids, in particular adamantane
and its derivatives, is their lipophilicity. This means that they can
be easily be taken up by lipidic membranes in cells. Consequently,
in the case of drugs that are not readily absorbed by cells, when
 Possible Applications in Chemistry, Pharmaceutics, Medicine, and Biotechnology 93

attached to diamondoid units, their incorporation in the organism

can be increased.
Because of the well-defined structure and surface chemistry
of diamondoids, they are attractive as bonding sites of functional
groups. When adamantane or other diamondoids are functionalized
by short peptide sequences, these can act as binding sites for
different types of macromolecules: proteins, nucleic acids, lipids,
and polysaccharides, to name a few examples.
Several examples of the application and potential of adamantane
derivatives acting as vectors for drug delivery have also been demon-
strated. One was the increased uptake of various azidothymidine
(AZT) drugs attached via an ester spacer to 1-adamantyl (Tsuzuki
et al., 1994). Compared to the same drug without the 1-adamantyl as
vector, its uptake in the brain tissue was increased by a factor varying
from 7 to 18.
In recent years, it has been found that commercial nanodiamond
particles produced by detonation synthesis and possessing diame-
ters of approximately 5 nm are interesting for biotechnological and
medical applications because of their low cell toxicity, biocompat-
ibility, and structural stability. Furthermore, because their surface
chemistry can be adjusted, they are attractive as bases for the
attachment of functional groups, making them attractive as drug
delivery systems.
As has been shown in Section 2.6, the surface chemistry of
nanodiamonds can be very diverse and they have to be tailored
by different surface treatments such as oxidation. To attach drugs
to nanodiamonds, different mechanisms are possible. These can
either be covalent bonding or adsorption, the type of bonding
often depending on the purpose of the intended application. For
drug delivery, adsorption/desorption processes are often preferred
because they are simple and they do not involve any change in the
molecular structure of the drug that would take place in the case of
covalent binding.
Additionally, the adsorption of drugs (especially those that are
only poorly soluble) on nanodiamonds offers also the advantage
that they can be taken up more readily by the organism. This is in
part due to the biocompatibility of nanodiamonds and the higher
exposure of the drug to the aqueous environment: A monolayer of
94 Current and Future Applications of Diamondoids and Their Derivatives

drug adsorbed on a nanodiamond particle offers maximal exposure

compared to a monocrystal of the same drug.
However, especially for cancer treatment, the binding of the
drug to the nanodiamond has to be well controlled in order to
avoid overloading of the organism by the drug in the case of strong
adsorption, or premature release of the drug that could lead to
side effects. Recent studies (Mochalin et al., 2013) have therefore
investigated in detail the binding strength of drug molecules to
nanodiamonds, in addition to desorption heat and kinetics. Other
factors that have to be taken into account for the application of
nanodiamonds as drug delivery systems are the role of pH, the ionic
composition of the fluid, nanodiamond purity and dispersion, and
the surface chemistry.
While nanodiamonds have been applied for various applications
in medicine and biotechnology, for example, blood cleansing and
sorption of heavy metals, dyes, proteins, toxins, and viruses,
only little is known about the fundamental adsorption/desorption
thermodynamics and kinetics of nanodiamonds.
A recent study showed that the adsorption of drugs strongly
depends on their surface chemistry and purity.
Currently, there are no studies available on higher diamondoids,
similar in size to nanodiamonds, that could have acted as drug
delivery systems, it is surmised that because of the well-defined
molecular structure and surface terminations, diamondoids could
alleviate some of the difficulties encountered in the use of
nanodiamonds, especially control of the surface chemistry and size
distribution.

4.4 Applications in Materials Science and

Nanotechnology
4.4.1 Materials Science
Because of their high thermal stability, diamondoid derivatives are
used increasingly as additives in various materials to improve their
properties. For example, Idemitsu Chemicals Co. is selling various
adamantane derivatives under the generic name AdamantateTM .
 Applications in Materials Science and Nanotechnology 95

a
O Adamantate™ MM: R = Me
R

O
Adamantate™ EM: R = Et

b
O Adamantate™ HA: R = H

O
HO R Adamantate™ HM: R = Me

Figure 4.7 Examples of adamantane derivates commercialized under the

name AdamantateTM and used in various application ranging from panel
displays to photoresists. (a) AdamantateTM MM and EM. (b) AdamantateTM
HA and HM. The abbreviation Me stands for methanol and Et for ethanol.

Using AdamantateTM as a base resin, superior characteristics

such as increased heat resistance, stiffness, and transparency
can be added to a variety of products including flat-panel
displays and photoresists used in semiconductor manufactur-
ing (cf. www.idemitsu.com/products/petrochemicals/chemicals/
adamantate.html). Figure 4.7 displays the molecular structure of
these adamantane derivatives.
The potential of diamondoids for nanotechnology, especially for
electron emission, has been recognized recently (Drummond, 2007).
In addition to this, because of the thermal stability, diamondoids
have been used to improve thermal resistance of polymers. One
example is the development of high-temperature polymers incor-
porating diamantane (Malik et al., 1991). Another example is the
incorporation of diamondoids in photopolymers such as SU-8 to
form a nanocomposite polymer (Chiamori et al., 2008).
In addition to adding stability to polymers, diamondoids have
also been suggested as subnanosized molecular building blocks. For
example, functionalized adamantane was proposed as blocks for
building self-assembled nanostructures (Garcia et al., 2009). The
same group also carried out numerical simulations to investigate the
possibility of boron- and nitrogen-functionalized diamondoids for
96 Current and Future Applications of Diamondoids and Their Derivatives

self-assembly (Garcia et al., 2010b), especially adamantane (Garcia

et al., 2010a).
The effect of nanoscale diamondoids on the thermomechanical
and morphological behaviors of polypropylene and polycarbonate
was studied by Ghosh et al. (Ghosh et al., 2007).
A recent review paper explores the possibility of diamondoids for
forming self-assembled monolayers (SAMs) in detail (Hohman et al.,
2010). Finally, diamondoids have been suggested as a means to form
advanced composites (Hu et al., 2006). Derivatives of adamantane,
such as AdamantateTM , are used as additives in photoresists to in-
crease the thermal resistance and by incorporating diamondoids in
metallic coatings, the wettability could be increased (Schwertfeger
and Schreiner, 2010).
A few of these examples will be examined in more detail in
the following sections. While many of these examples are mainly
numerical simulations, there are a few cases where the potential of
diamondoids for certain applications has also been demonstrated by
experiments.

4.4.2 Diamondoids as an Electron Source

Diamondoids could also be used as semiconductors possessing
negative electron affinity (NEA). Previously, it has been reported that
large-area SAMs of a functionalized diamondoid, [121]tetramantane-
6-thiol, could be used for highly monochromatic electron photoemis-
sion (Yang et al., 2007). Figure 4.8 shows the molecular structure of
[121]tetramantane-6-thiol and a schematic of an SAM, and typical
photoemission spectra for [121]tetramantane-6-thiol SAMs on Au
and Ag are displayed in Fig. 4.9a and 4.9b, respectively.
Work by Willey et al. (Willey et al., 2008) has shown that
the diamondoid monolayer structure and thiol substitution can be
controlled, permitting to change the electronic structure of the
SAMs.
The mechanism behind the monochromatic photoelectron emis-
sion was investigated more in detail by Clay et al. (Clay et al., 2009)
and is shown schematically in Fig. 4.10. The authors found that the
reason for monochromatic photoelectron emission of diamondoid
SAMs is that like diamond, diamondoids possess NEA. It has been
 Applications in Materials Science and Nanotechnology 97

Diamondoid SAM
~30º

Metal
(Ag, Au)

[121] tetramantane-6-thiol

Figure 4.8 Molecular structure of [121]tetramantane-6-thiol and

schematic of self-assembled monolayers. Near-edge X-ray absorption fine
structure (NEXAFS) measurements revealed that the orientation of the
[121]tetramantane-6-thiol molecules, that is, the angle measured between
the S−C bond and the surface normal, had values of 30 ± 10◦ .

a b
Intensity (arb. unit)
Intensity (arb. unit)

Log

Log

0.1 1.0 10.0

Log 0.1 1 10
Log
×50 ×3

0 10 20 30 40 50 0 10 20 30 40 50
Kinetic energy (eV) Kinetic energy (eV)

Figure 4.9 Photoelectron emission spectra of [121]tetramantane-6-thiol

self-assembled monolayers (SAM). (a) Emission for Ag SAM. (b) Emission
for Au SAM. In both graphs, the dotted lines represent the data that has been
enlarged by ×50 for Ag and ×3 for Au to enhance the features of the valence
bands. Data adapted from Yang et al. (2007).

found that SAMs of [121]tetramantane-6-thiol on Au or Ag films

have quantum yields larger than unity.
The NEA of diamondoids results from unoccupied states in
the lowest unoccupied molecular orbitals (LUMOs), which, when
populated by an electron, directly leads to spontaneous electron
emission (Roth et al., 2010). In contrast to Si and Ge nanoparticles,
98 Current and Future Applications of Diamondoids and Their Derivatives

E
Ekin 2
3
Electron emission

5 4

Photoelectron yield Evac

EF (Au)

1
hν

Diamondoid SAM Metal substrate

Density of states

Figure 4.10 Mechanism of photoelectron emission from diamondoid self-

assembled monolayers. Schematic of the currently understood processes
leading to spontaneous photoelectron emission: 1 electrons are excited by
photon and excited to unoccupied states with E > E f , 2; 3 thermalization
of electrons to lower-energy levels; 4 electrons with E > E CBM move to
diamondoids; 5 by transitioning to lower-energy levels and accumulating
at the bottom of the conduction band, these electrons excite phonons in
the diamondoid molecules and, as a consequence of the negative electron
affinity, transfer into vacuum. E f : Fermi level of gold (Au) substrate;
E vac : vacuum level; E kin : kinetic energy; E CBM : conduction band minimum.
Adapted from Yang et al. (2007).

where the LUMO is core confined, the LUMO of diamondoids is

a delocalized surface state (Drummond et al., 2005). The charge
transfer mechanism that allows the electron to be promoted from
the metal into the diamondoid LUMO is very efficient, and electrons
are emitted almost instantaneously with an upper bound of a few
femtoseconds. This suggests that if suitable pulsed light sources are
available, diamondoid SAMs could be used as ultrashort (∼fs), high-
brilliance pulsed electron sources for use in electron microscopy,
electron beam lithography, field-emission flat-panel displays, and
photocathodes.
Investigations of diamondoids up to [121]-tetramantane also
showed that the dielectric constant κ is about half the one of bulk
 Applications in Materials Science and Nanotechnology 99

diamond (κ ≈ 5.6), ranging from 2.46 for adamantane to 2.68 for

tetramantane (Clay et al., 2008). This suggests that diamondoids
could be new candidates as low-κ materials for microelectronics
applications.
Using the negative electron affinity properties of diamondoids,
a photocathode device using diamondoid and bromide films has
been demonstrated recently (Clay et al., 2012). The photoyield of the
diamondoid/bromide films was higher and more stable compared to
the diamondoid-only films.
It has also been shown that the bandgap of diamondoids can
be tuned by either changing their size or changing functional
groups (Fokin and Schreiner, 2009). The authors conducted an
extensive density functional theory (DFT) study for elucidating the
effect of different doping strategies on the bandgap of diamondoids.
The approaches they investigated were the enlargement and chang-
ing of the shapes/morphologies of the particles, the effect of C−H
bond substitutions with various functional groups (external doping),
and finally the effect of incorporating heteroatom functionalities of
one or more alkylated terminations such as CH or CH2 fragments
(interstitial or internal doping).
They found that by increasing the size of diamondoids from
C10 H16 (adamantane) to about 2 nm (C286 H144 ), the bandgap
decreases from 6.7 eV, which is still larger than the bandgap of bulk
diamond (5.5 eV). It was also found that it is the size and not the
morphology that influences the bandgap most.
In their paper, the authors discovered that bandgap tuning
through external (by C−H bond substitution) or internal doping
(by replacing CH or CH2 groups) is nonadditive for the same
dopant. This means that, for instance, doubling the number of
same functional groups does not lead to a linear decrease in
the bandgap. Functionalization by attaching electron-donating and
electron-withdrawing groups (push-pull doping) was found to be
most effective and permitted to reduce the bandgap of diamondoids
to that of bulk diamond.
Sasagawa et al. (Sasagawa and Shen, 2008) studied the effect of
clustering on the bandgap. DFT calculations showed that in contrast
to bulk diamond, crystalline adamantane has a direct bandgap. As
the transition of electrons across the bandgap can accompany the
100 Current and Future Applications of Diamondoids and Their Derivatives

absorption and emission of photons, the efficiency of this process

can be expected to be far better in crystalline diamondoid materials
compared to indirect-bandgap materials.

4.5 Possible Future Applications of Diamondoids

It is expected that because of their well-defined structure and high
stability, diamondoids could also be used in many different other
applications in the future.
In the following section, we will present a few examples of
promising research involving the use of diamonds or nanodiamonds
that could potentially be replaced by diamondoids.
This research includes photonics but also the field of quantum
communication and computing. Macroscopic diamond has been
hailed as a material that can match the requirements of the second
quantum revolution (Aharonovich et al., 2011). As will be shown in
detail in the following section, sufficiently large diamondoids that
contain nitrogen vacancy (NV) centers could replace currently used
diamonds for some of these applications. Figure 4.11 illustrates a
diamond unit cell containing such an NV center.

N
V

Figure 4.11 Crystallographic structure of nitrogen vacancy center in

diamond. The vacancy (V) is surrounded by a single nitrogen (N) and three
carbon atoms (C). Adapted from Mizuochi et al. (2012).
 Possible Future Applications of Diamondoids 101

In subsequent sections, we will also briefly discuss the possible

use of diamondoids as molecular building blocks in exotic sounding
applications such as nanorobots and molecular machines.
While actual implementation of nanorobots and molecular
machines still has to be demonstrated, we believe that the structural
stability and well-defined shapes of diamondoids make them ideal
building blocks for such applications.

4.5.1 Biotechnology
One of the key breakthroughs in understanding cell processes
has been the real-time imaging of cell dynamics. Recent studies
have demonstrated 3D tracking of single fluorescent nanodiamonds
inside cells, as well as preliminary experiments of imaging living
cells, drug delivery, and targeted bioimaging. As mentioned in
the previous section, the recent discovery of new ultrabright
colour centres with narrow emission in the near-infrared region is
significant for such tracking techniques, as these wavelengths do not
interfere with cell autofluorescence. However, no mass production
technique yet exists that can incorporate such bright emitters into
nanodiamonds (Aharonovich et al., 2011).
For example, chemically modified diamondoids have been
suggested as potential biosensors for DNA testing (Sivaraman and
Fyta, 2014). So far, mainly nanodiamonds have been used for
investigating cellular mechanisms, which is evident from the large
number of texts in the literature.

4.5.2 Quantum Computing and Communication

In recent years, advances for future access of both quantum
communication and computation have increased considerably.
Conventionally, to entangle spins over large distances, it has
been necessary to work at very low temperatures of a few
Kelvin. However, in recent years, alternative approaches have been
proposed. It has been found that diamonds containing permanent
spins, caused by NV centers, that is, the presence of nitrogen
impurities and carbon vacancies, permit spin entanglement at room
temperature. A schematic of a diamond crystal lattice containing
102 Current and Future Applications of Diamondoids and Their Derivatives

such an NV center is shown in Fig. 4.11. This NV defect represents

a permanent spin that has been shown to be useful for different
applications, such as small magnetic probes.
Up to now, the potential for application in quantum communica-
tion and quantum computing has been shown for macrodiamonds
with sizes of a few millimeters. However, nanodiamonds possessing
a single NV have also been reported (Aharonovich et al., 2011).
One could imagine that such diamonds that are currently of several
millimeters could be replaced by nanodiamonds or even higher-
order diamondoids. However, currently, it is also not known how
large such diamondoids would have to be so that their structure
and consequently also the NV color centers are sufficiently stable
for spin entanglement. Currently there are no studies that have
investigated the effect of diamondoid size on the stability of NV color
centers, that is, to determine what would be the smallest necessary
size of a diamondoid to accommodate an NV center. It would be
interesting, both from a theoretical and from a practical point of
view, to investigate this in the future.
In addition to quantum computing and communication appli-
cations, diamondoid-like porous networks could also be used for
molecular shape sorting (Mitra et al., 2013).

4.5.3 Magnetometry
Investigating magnetism at the nano- and atomic scale is a key issue
both for understanding fundamental physical properties of matter
and as the enabling ingredient for magnetism-based data storage
and spintronic devices (Degen, 2008).
The NV centers in diamond have been shown to be useful for
measuring very small magnetic fields.
A disadvantage of magnetic resonance force microscopy (MRFM)
is that it only performs well at cryogenic temperatures and in
vacuum, which is not compatible with many biological (and other)
applications. Therefore we are trying to come up with other ideas
that might allow us to do the same experiments under ambient
conditions.
In scanning diamond magnetometry, quantum optics is used to
detect minute magnetic signals from samples via the fluorescent
 Possible Future Applications of Diamondoids 103

light emitted by NV centers in diamond. As already mentioned, such

NV centers carry a spin, which is very sensitive to magnetic fields.
As the optical rate of emission depends on the defects spin state,
small magnetic fields can be measured by looking at the fluorescence
intensity (Degen, 2008; Taylor et al., 2008).
Placing a diamond defect in a nanocrystal and attaching it to a
scanning probe allows performing imaging at the nanometer scale.
The big advantage is that such scanning diamond magnetometers
have the capability to measure the dipole field of single-electron
spins, or monolayers of organic materials containing proton spins,
at room temperature. The combination of diamond sensors with
magnetic resonance spectroscopy allows realizing of the chemi-
cal analysis of surfaces (organic, metallic, etc.) with nanometer
resolution.

4.5.4 Nanorobots and Molecular Machines

Because of their high thermal stability compared to other organic
molecules such as alkanes, diamondoids might be useful as building
blocks for nanorobots and in molecular machines.
Rotary dynamics at the molecular level hold promise for various
applications, and the effects of rotational symmetry on the dynamics
of a molecular rotor consisting of phenylene and diamantane has
been investigated (Karlen et al., 2005).
The advantage of diamondoids is that compared to other rigid
molecular structures that could be candidates for molecular rotors,
they possess higher cylindrical symmetries. For example, in the case
of structures possessing C n symmetries with n > 2, there are n
energy minima and 360◦ /n angular displacements. An example of
such a molecular rotor is displayed in Fig. 4.12.
Based on different diamondoids, basic toolsets for diamond
mechanosynthesis were defined. These include parts for abstracting
hydrogen and also to attach other molecules. A minimal set of
such a diamondoid-based mechanosynthesis toolset is presented in
Fig. 4.13, and Fig. 4.14 shows the application of the HABst tool for
removing a hydrogen atom from a (111) diamond surface.
In the wake of nanotechnology, bottom-up approaches have
also been proposed to be applicable for medical applications,
104 Current and Future Applications of Diamondoids and Their Derivatives

Figure 4.12 Diamondoids as building blocks for molecular robots. Molecu-

lar structure of 4,9-bis(4-iodo-phenyl) diamantane that can serve as a rigid
rotor.

so-called nanomedicine. One of the hallmarks of nanomedicine,

as proposed by several researchers, is the treatment of diseases
directly in the body or cells. To make this possible, the use of
nanorobots has been proposed (Patel et al., 2006). Because of their
advantageous properties and as an extension of diamondoid-based
mechanosynthesis, it has also been suggested that diamondoids
could be used to fabricate nanorobots that could be used for medical
applications (Freitas, 2009).
 Summary 105

Tool
HAbst HDon HTrans DimerP

Handle
AdamRad GeRad Methylene GermyleneMethylene Germylene

Figure 4.13 Minimal diamondoid toolset. Adapted from Freitas (2009).

HAbst tool

Diamond (111)

Figure 4.14 Hydrogen abstraction via mechanosynthesis. A hydrogen

termination is removed from a diamond (111) surface by the use of the
HAbst tool. Adapted from Freitas (2009).

4.6 Summary
As has been outlined in this chapter, the well-defined structure of
diamondoids, which distinguishes them from nanodiamonds, makes
them predestined for use as molecular building blocks in a wide
range of applications. The highest potentials for the application
of diamondoids is certainly in medicine and biotechnology, where
adamantane derivatives have already been used to treat Alzheimer’s
106 Current and Future Applications of Diamondoids and Their Derivatives

and Parkinson’s diseases and have also acted as the bases for other
drugs.
In addition to these applications, diamondoids that contain
structural defects, namely NV centers, could be useful for spintronic
applications and quantum computing and quantum communication.
However, while certain physical properties of diamondoids have
already been demonstrated experimentally, the main problem is
their (non)availability, especially that of higher diamondoids with
n ≥ 4, in large quantities.
In the following part, the methods used up to now for obtaining
diamondoids, either by isolation from natural gas and oil reservoirs
or by organic synthesis, are presented.
 PART II

ISOLATION AND ORGANIC CHEMICAL

SYNTHESIS OF DIAMONDOIDS
Chapter 5

Occurrence and Isolation of

Diamondoids from Natural Gas and Oil
Reservoirs

The topic of this chapter is the isolation of diamondoids from natural

sources, namely gas and oil reservoirs. We briefly present a short
history of their discovery from the 1930s to the present date and
the techniques necessary for their isolation and purification that
were developed following the isolation of higher diamondoids up to
undecamantane in the 1990s.

5.1 Occurrence of Diamondoids in Natural Gas

and Oil Reservoirs
The first member of diamondoids, adamantane, was first found in
crude oil in 1933 in Czechoslovakia in the region of Hodonin. Since
then, diamondoids have been discovered in a variety of gas and oil
reservoirs, including Japan (Shimoyama and Yabuta, 2002). While
diamondoids are thermally stable, it has been found that over time,
and if the temperature is above the peak diamondoid formation

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
110 Occurrence and Isolation of Diamondoids from Natural Gas and Oil Reservoirs

temperature of about 340 K, they can decompose again (Schoell and

Carlson, 1999).
To understand the formation of diamondoids in natural sources,
attempts have also been made to draw parallels with nanodiamond
formation using explosives (Pichot et al., 2013). Since diamondoids
often lead to fouling of the piping during oil or gas exploration, that
is, when they form solid condensates, over the years methods to iso-
late and separate them from crude oil have been developed (Huang
et al., 2011).
The importance of diamondoids in natural fossil sources,
including oil, has long been recognized, and also the implication
of the presence of diamondoids on the structure of coal has been
investigated (Aczel et al., 1979).
There have also been attempts to understand the reactions of
diamondoids, especially alkylated adamantanes, in sediments, and it
has been suggested that carbon surface reactions play an important
role (Berwick et al., 2011).
Besides natural oil and gas reservoirs, traces of diamondoids
have also been found in meteorites, which would imply that
diamondoids were also formed in the early solar system (Dai et al.,
2002). Moreover, signs of diamondoids have also been detected in
carbon-rich proto-planetary nebulae (Hill et al., 1998). Finally, it
has been suggested that diamonds, including diamondoids, could
be of presolar origin, which was found by comparing samples of
meteoritic and terrestrial origin by high-resolution transmission
electron microscopy (Daulton et al., 1996).
Catalytic and thermal cracking of pure hydrocarbons in oil and
gas reservoirs has been investigated since the 1940s (Greensfelder
et al., 1949). After the first discoveries of adamantane in oil sources,
diamantane also could be isolated from petroleum (Hala et al.,
1966).
Finally, it has also been surmised that not only diamondoids but
also macrodiamonds could be found in crude oil (Hopf, 2003).
In normal gas and oil reservoirs, the contents of diamondoids
is of the order of ppm or even sub-ppm (Liang et al., 2012), but
the concentration increases with the degree of oil cracking, which
is associated with depths within the earth of about 5 km and
 Formation of Diamondoids in Natural Sources 111

temperatures of 150◦ C–175◦ C, the so-called oil deadline. Because

of their high thermal stability, diamondoids can serve as indicators
for the amount of oil cracking. Dahl et al. (Dahl et al., 1999)
investigated the concentration increase of methyldiamantane as a
function of cracking of oil to gas and pyrobitumen increases dia-
mondoid concentration. The concentration of methyldiamantanes
in uncracked oils—the diamondoid baseline—is on the order of
1–10 ppm, depending on the source(Dahl et al., 1999).
Biomarkers are molecular fossils that possess recognizable
carbon structures of natural products and that are synthesized by
oil precursor organisms such as bacteria and algae.

5.2 Formation of Diamondoids in Natural

Sources
In this section, we will give a brief overview of the processes
that lead to the formation of diamondoids in natural gas and oil
reservoirs.
As will be explained in more detail in later sections, with the
exception of the lower diamondoids adamantane and diamantane,
currently the main sourced of higher diamondoids are natural oil
and gas reservoirs, while especially conventional organic chemical
synthesis methods have been demonstrated to be limited by the
many different possible reaction pathways, reaction intermediates,
and local minima on the potential energy surface.
Understanding the natural processes of diamondoids in natural
sources and the conditions under which the formation of diamon-
doids is highest might also help to improve artificial synthesis of
diamondoids.
Both gas and oil are produced from organic matter. Almost all,
that is, more than 99% of the organic matter which is produced
on land or in the oceans is dissociated by direct oxidation or by
microbiological processes.
Figure 5.1 illustrates schematically the carbon cycle and the
region where the main precursor of diamondoids, kerogens, are
formed.
112 Occurrence and Isolation of Diamondoids from Natural Gas and Oil Reservoirs

Dissolution of
CO2 carbonate rocks
CO
Photosynthesis
CO2
Oxidation of
organic matter Addition of organic CO2
matter and nutrients
Transport of Delta to the ocean exchange
organic matter
(rivers) Organic Photosynthesis
plant matter Breakdown
in delta of biogenic CO2
sediment carbonate
Oxidation of
Deposition organic matter
of carbonate
CO2
Oxidation and CO2
biological Ocean floor
processing of
organic material
C Deposition of organic
material
CO2
Kerogen in sediments

Carbon in sedimentary rocks

Figure 5.1 Illustration of the carbon cycle. Carbon from organic matter
and carbonate rocks are the major sinks for carbon (CO2 ). The rate of
precipitation of carbonate in the ocean by organisms is limited by the supply
of Ca ++ and Mg ++ from weathering of silicate rocks brought in by rivers.
The illustration also shows where the main precursors of diamondoids,
kerogens, are formed. After Bjørlykke (2010).

As organic material, both from plants and from organisms,

becomes buried by the accumulation of sediments, water is
gradually expelled during compaction. Complex organic compounds
like proteins are broken down into amino acids, while carbohydrates
transform into sugar compounds. These smaller compounds are able
to recombine to form larger compounds, for example, by amino acids
reacting with carbohydrates (melanoid reaction) (Bjørlykke, 2010).
As this type of polymerization proceeds, the proportion of simpler
soluble organic compounds diminishes at depths of a few tens of
meters down in the sediment. These newly formed complex organic
structures are called kerogens. In short, kerogen is a collective term
for organic material that is insoluble in organic solvents, water, or
oxidizing acids. Kerogen consists of very large molecules and is
therefore similar to macromolecules or polymers. When kerogens
 Formation of Diamondoids in Natural Sources 113

0
Type I Type II Type III
1000 30
Burial depth (m)

2000 60

Temperature (ºC)
Oil
Oil
3000 90

4000 Oil 120

5000 Gas Gas 150

Gas

6000 180
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 0 0.2 0.4
Oil and gas generated (% of total C)

Figure 5.2 Oil and gas formation as a function of temperature and depth.
Data adapted from Vandenbroucke (2003).

are exposed to elevated temperatures, the large molecules crack

into smaller ones, predominantly petroleum. At temperatures of
about 100◦ C, long geological times are required for this process. In
reservoirs that are sinking rapidly, the exposure time is shorter and
oil generation can only start at about 140◦ C to 150◦ C. Figure 5.2
indicates the depth and temperature conditions for the formation
of oil and gas.
Figure 5.3 displays the variation of the diamondoid content
(adamantane, diamantane, and derivatives) as a function of EasyRo
in percent. EasyRo (also written as EASY%Ro ) is a model (Sweeney
and Burnham, 1990) that allows predicting the level of vitrinitea
maturation, that is the change in the level of vitrinite in a given
sedimentary rock as a function of time and temperature. As can be
seen in the figure, the maximum is reached at about 2.0 EasyRo.
It has also been found that diamondoids are more abundant
in reservoirs that contain clay minerals, especially montmorillonite
(K10), whose structure is depicted in Fig. 5.4. To investigate the
influence of the presence of clay minerals on the formation of

a Vitrinite is an organic coal and kerogen component and has a shiny appearance
similar to that of glass.
114 Occurrence and Isolation of Diamondoids from Natural Gas and Oil Reservoirs

a 250
 A
 MA
200   DMA

Yield g g  1 

TMA
150   EA



100 





50  
 


   








 
 
  

0 



 

 



 
    
 
 

0 1 2 3 4
EasyRo (%)
b 250
 D
200
 MD
Yield g g  1 

150  DMD

100 


50     

   
    
0   
 
 


0 1 2 3 4
EasyRo (%)

Figure 5.3 Variation in the yields of diamondoids with EasyRo (%) in the
oil- cracking experiment. The yields are given in μg g−1 oil. (a) Adamantanes
and (b) diamantanes. A, adamantane; MA, methyladamantanes; EA, ethy-
ladamantanes; DMA, dimethyladamantanes; TMA, trimethyladamantanes,
D, diamantane; MD, methyldiamantanes; DMD, dimethyldiamantanes. Data
adapted from Fang et al. (2012).

diamondoids, Moldowan and coworkers conducted a series of

experiments. These consisted of using diamondoid precursors such
as kerogens and sealing them in vessels that were heated to
temperatures typical of oil formation.
However, while diamondoids can grow at temperatures between
150◦ C and 250◦ C, if they are outside this temperature window, then
 Isolation of Diamondoids from Gas and Oil 115

O
Si
O, H
Al (or Mg, Fe (II, III), Li+)
O, H
Si
O

Interlayer distance d ≈ 0–4 nm

O
Si
Al

Figure 5.4 Crystal structure of montmorillonite, K10. Depending on

the type of montmorillonite, the layers can exhibit different chemical
compositions. The interlayer distance d depends on the type and amount
of absorbed molecules.

they can decompose again. In addition, it has also been found that
diamondoids can be decomposed by certain bacteria.

5.3 Isolation of Diamondoids from Gas and Oil

From a practical point of view, for oil and gas exploration, the
presence of diamondoids is not desirable, as they often form con-
densates, clogging piping systems. In order to separate diamondoids
from oil or gas condensates, several steps are necessary (Dahl
et al., 2003a). First, the oil condensates are distilled under
vaccum at temperatures above 345◦ C. In a next step, pyrolysis at
T = 400◦ C–450◦ C is used to remove nondiamonds from the mixture.
Then, silica gel liquid chromatography is employed to remove
aromatic and polar compounds, and finally, reverse-phase high-
performance liquid chromatography (HPLC) is used to separate the
diamondoids, and shape selective HPLC can be used to differentiate
diamondoid enantiomers. The flowchart illustrating the diamondoid
separation process is illustrated in Fig. 5.5.
116 Occurrence and Isolation of Diamondoids from Natural Gas and Oil Reservoirs

Oil condensates

Vacuum distillation > 345 ºC

Pyrolysis 400−450 ºC Removal of

nondiamondoids

Removal of aromatic
Argentic silica gel
and polar compounds
liquid chromatography

Separation of
Reverse-phase HPLC higher diamondoids

Separation of
Shape-selective HPLC enantiomers

Recrystallization

Figure 5.5 Schematic of the separation process for obtaining single

crystals of higher diamondoids. Oil condensates are concentrated by
vacuum distillation at temperatures above 345◦ C. Volatile components and
nondiamondoids are cracked by pyrolysis conducted in the temperature
range of 400◦ C–450◦ C. In the next step, polar and aromatic compounds
are removed by silica-gel-based column chromatography. Individual types
of higher diamondoids are isolated by reverse-phase HPLC, enantiomeric
diamondoids being separated by shape-selective HPLC. The separated
fractions are finally recrystallized.

5.3.1 Alternative Purification Methods

As an addition to the original isolation and purification pro-
cess (Dahl et al., 2003a), a more advanced refinement method
using a two-zone furnace for the growth of large single crystals of
diamondoids by the so-called vapor transport technique has been
developed (Iwasa et al., 2010). In this method, by taking advantage
of the low binding energy due to weak van der Waals forces and
the low sublimation temperatures of diamondoids, the sample is
 Isolation of Diamondoids from Gas and Oil 117

a Transparent heating units b

300 ºC 250 ºC 0.07
0.06

Sealed quartz tube 0.05

Log (I0/I)
400 0.04
Crude powder
350 0.03
Grown
T (ºC)

300 crystal 0.02

250 0.01

200 200 300 400 500 600

100 50 0 50 100
Wavelength (nm)
Position (mm)

Figure 5.6 Schematic of the two-zone furnace used for refinement and
crystallization of diamondoids. (a) Two-zone furnace consisting of a quartz
tube and a thin wire that acts as a heating element. (b) Absorbance spectra
of commercial and refined diamantane dissolved in n-hexane. The reduced
intensity of the absorbance peak at λ ≈ 260–280 nm in the refined sample
indicates the decrease of impurities. Schematic of furnace and data adapted
from Iwasa et al. (2010).

first brought in the vapor phase by heating of one end of the tube.
The particles brought into the vapor phase then deposit in different
zones along the tube.
This method allows to obtain high-quality diamondoid crystals
without having to resort to other purification techniques such as
multistage distillation or high-performance liquid chromatography
(HPLC), and it is possible to obtain diamondoid single crystals with
volumes up to ∼1 cm3 and to reduce the number of impurities
considerably.
Figure 5.6a shows a schematic of the two-zone furnace and the
temperature distribution along the axis of the sealed quartz tube.
The crystals recrystallize in the zone with the lowest temperature.
Figure 5.6b shows a comparison between absorption measurements
of a commercially available and a refined diamantane sample.
Chapter 6

Approaches for the Organic Synthesis of

Diamondoids

In this chapter, we give a short overview of the currently known

routes for synthesizing diamondoids using chemical synthesis
approaches, without the pretension to be fully exhaustive, as
there is a large body of research literature available, to which
the reader will be pointed. As will be explained in detail, the
complexity in synthesizing diamondoids grows exponentially with
an increasing cage number, and to date, there are only methods
that allow obtaining all the lower diamondoids—adamantane,
diamantane, and triamantane—and one higher diamondoid, anti-
tetramantane. We also summarize the currently known main
procedures for their functionalization, before closing this chapter
with a short section on the difficulties and limits related to
the synthesis of diamondoids by conventional organic chemical
synthesis.

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
120 Approaches for the Organic Synthesis of Diamondoids

6.1 A Brief History of the Isolation and Organic

Synthesis of Diamondoids
As mentioned in Chapter 2, the structure of adamantane based on
the diamond lattice was predicted already at the end of the 19th
century.
An extensive account on the history of the synthesis of lower
diamondoids is given in the paper by Schwertfeger et al. (2008), and
here, we briefly summarize the main points. As has already been
mentioned in Chapter 5, the structure of adamantane was already
predicted before it was isolated for the first time from crude oil in
Hodonin in former Czechoslovakia in 1933.
The first artificial synthesis of adamantane was reported
by (Prelog and Seiwerth, 1941a), but the yield was very low, only
on the order of a few percent. Especially in the 1950s and 1960s,
research on the synthesis of diamondoids became very active, and
several methods were developed to obtain diamondoids up to
antitetramantane.
Following the synthesis of the lower diamondoids in reasonable
yields, the organic synthesis of higher diamondoids was the topic of
further intensive efforts up to the early 1980s. However, it could be
demonstrated that while lower diamondoids can be synthesized by
carbocation equilibration reactions, this approach does not work for
higher diamondoids.
Other problems that prevented successful synthesis of higher
diamondoids were the lack of suitable precursors, the rapidly
growing number of possible isomers, intermediates being trapped
in local energy minima, and the formation of unwanted side
products. As a result, research on carbocation-mediated syntheses of
diamondoids beyond tetramantane was abandoned at the beginning
of the 1980s (Osawa et al., 1980), and up to now, only one of the
higher diamondoids, [121]tetramantane, has been synthesized, but
the reaction is complex and the reaction yields very low (Burns et al.,
1978).
The interest of diamondoids was only renewed when it was
reported that diamondoids with a number of cages (n) of up
to 11 were isolated from crude oil (Dahl et al., 2003a) (see
 Conventional Organic Chemical Synthesis of Diamondoids 121

Chapter 5). Since then, work on diamondoids, both experimental and

theoretical, has increased again.
In the next section, we will discuss the approaches used for the
organic synthesis of diamondoids in detail.

6.2 Conventional Organic Chemical Synthesis of

Diamondoids
As has been outlined in the previous section, since the discovery of
the first diamondoid members adamantane and diamantane, many
attempts have been undertaken to obtain diamondoids synthetically.
In this section, we treat the synthesis of diamondoids from
adamantane up to tetramantane in more detail, but we also refer
the interested reader to detailed works in the literature. As will be
seen, the complexity of the diamondoid reactions increases with the
number of diamondoid units, while the reaction yields, especially for
diamondoids above diamantane, decrease.
What will also become evident from this section is that both
adequate precursors and catalysts are crucial for obtaining the
desired structures. We close this section with a brief explanation on
why, currently, there are no known successful approaches that would
allow the facile synthesis of diamondoids larger than tetramantan in
sufficient yields.

6.2.1 Synthesis of Adamantane

The structure of adamantane was already predicted at the end of the
19th century, but it was only in 1933 when it was first isolated from
oil in Hodonin in today’s Czech Republic. Since the discovery, various
attempts have been made to synthesize adamantane by different
means and while the first approaches gave only small yields, more
effective reaction schemes were developed over time. In this section,
we will present the currently most commonly used approaches for
the synthesis of adamantane.
While originally, all the smaller diamondoids were isolated from
crude oil, nowadays adamantane is predominantly synthesized by
122 Approaches for the Organic Synthesis of Diamondoids

H2 / PtO2 AlCl3

Et2O 150–180 ºC

Figure 6.1 Reaction scheme for the synthesis of adamantane. Cyclopenta-

diene serves as a precursor, which is then hydrogenated to tetrahydrod-
icyclopentadiene using platinum dioxide (PtO2 ) and diethyl ether (Et2 O).
Using a strong Lewis acid (AlCl3 ), tetrahydrodicyclopentadiene can then be
rearranged to form diamantane.

conventional organic synthesis, and its production is on the order of

several tons per year.
The first report on the synthetic fabrication of adamantane dates
from 1941 (Prelog and Seiwerth, 1941b). In the same year, the
same authors further refined their approach, which allowed them
to increase the reaction yield from 2% to higher values (Prelog and
Seiwerth, 1941a).
There were also a few other attempts to synthesize adamantane
more effectively, but these approaches always required several
reaction steps and the yields were always only on the order of a
few percent. Then, an approach based on so-called stabilomeric
rearrangement of tetrahydrodicyclopentadiene by Lewis acids
allowed the synthesis of adamantane (Schleyer, 1957). This method
involves two reaction steps, which are illustrated in Fig. 6.1. This
method allowed reaching reaction yields of 12–13%.

6.2.2 Synthesis of Diamantane

The diamantane structure was chosen as the official emblem of the
XIXth International Congress of Pure and Applied Chemistry, which
was held in London in 1963, and the synthesis of congressane’, as
it was called, was sugggested as a challenge for the participants
of the congress. Following this challenge, a first approach was
first demonstrated two years after the congress (Cupas et al.,
1965). Figure 6.2 illustrates two possible synthesis methods for
the synthesis of diamantane. In both approaches, norbornene is
first converted photochemically in the presence of photosensitizing
agents (symbolized by hν in Fig. 6.2) to a norbornene dimer
 Conventional Organic Chemical Synthesis of Diamondoids 123

hν [Cat]

Cat:
1) AlCl3: 1%
2) AlBr3 / t-BuBr: 10−11%

Figure 6.2 Schematic of diamantane synthesis. The starting material is

norbornene, which is converted photochemically first to the norbornene
dimer (intermediate product between norbornene and diamantane). When
treated with a catalyst (“Cat”), in this case AlCl3 (method 1), tar but also
diamantane is produced. The yield of this reaction is on the order of
1%. When instead using AlBr3 and tert-butyl bromide (t-BuBr, method 2),
reaction yields up to 11% are obtained.

(C14 H20 ), whose structure is shown in the middle of Fig. 6.2. When
treated with AlCl3 (method 1), some isomers of this norbornene
dimer can give large quantities of tar, but others also give small
amounts of diamantane, of the order of 1% (Cupas et al., 1965). By
replacing AlCl3 with a mixture of AlBr3 and tert-butyl bromide (t-
BuBr, method 2), the reaction yields can be increased up to 11%
(Gund et al., 1970; Williams et al., 1966).
In addition to the reactions described in Fig. 6.2, various
alternative synthesis routes were explored in order to achieve
even higher reaction yields of diamantane. Figure 6.3 gives a few
more examples of such synthesis approaches, which are based on
basically three different precursors. The first is based on using
cyclopentadiene and the formation of a C14 H20 isomer as reaction
intermediate using different types of approaches (labeled methods
1–4 in Fig. 6.3a) (Gund et al., 1970). In Fig. 6.3b, the synthesis of
diamantane is achieved by using the so-called “Katz dimer” as a
precursor (Mrowca and Katz, 1966). Finally, Fig. 6.3c lists different
reaction schemes where “Binor-S” was used as a starting material.
Finally, Fig. 6.4 illustrates a few more alternative approaches for
the diamondoid synthesis. Figure 6.4a shows two possible methods
based on the use of cycloheptatriene as a precursor, which is then
dimerized with the aid of titanium complex catalyst. The following
step involves hydrogenation in the presence of platinum as a catalyst.
124 Approaches for the Organic Synthesis of Diamondoids

a
C2H5 [Cat]

1) Na / NH3
2) C2H5Br Cat:
3) norbornene, ∆ AlBr3 / t-BuBr; 30%
4) hν, acetone

b
H2, Pt [Cat], 150˚C
C14H20

Cat: Pt-Cl-alumina, HCl; 45 %

c
H2, Pt [Cat] (1-7)
C14H20

[Cat] (8)
Cat:
1) AlBr3, CS2 or cC6H12; 60-70%
2) Pt-Cl-alumina, HCl, 150˚C; 70%
3) CH2Cl2, AlCl3; 82%
4) H2SO4, 60˚C; 10%
5) B(OSO2CF3)3, Freon-113; 99%
6) CF3SO3H-SBF5 (1:1); 98%
7) CF3SO3H-B(OSO2CF3)3 (1:1); 98%
8) NaBH4, CF3SO3H, Freon-113; 99%

Figure 6.3 Alternative approaches for the synthesis of diamantane using

different types of precursors and catalysts. (a) Cyclopentadiene as a
precursor. (b) Katz dimer as starting material. (c) Binor-S as precursor and
using different types of catalyists (methods 1–8). The percentages listed
with the catalysts indicate the respective reaction yields and the symbol 
indicates the use of heat. Reaction schemes adapted from Schwertfeger et al.
(2008).

This approach leads to reaction yields of up to 89% of diamantane

(Schwertfeger et al., 2008).
The reaction scheme in Fig. 6.4b is based on the use of
spiro[2.4]hepta-4,6-diene as a precursor (Schwertfeger et al., 2008).
However, this approach does give diamantane yields of only 13% or
 Conventional Organic Chemical Synthesis of Diamondoids 125

a
H2 / Pt
AlCl3

Al(C2H5)2Cl, 89%
TiCl4 +
AlCl3
H2 / Pt
89%

b
∆ H2 AlBr3
13%

hv
H2 AlBr3
9%

c
AlBr3, CS2, 5h RT

94%

Figure 6.4 Alternative synthesis approaches for the synthesis of diaman-

tane. (a) With cycloheptatriene as precursor. (b) Spiro[2.4]hepta-4,6-diene
as starting material. (c) Using a pentacyclotetradecane (D3 -tritwistane) as
precursor. The percentages indicate the reaction yields. Reaction schemes
adapted from Schwertfeger et al. (2008).

9%. The reaction scheme depicted in Fig. 6.4c is based on the use
of a pentacyclotetradecane D3 -tritwistane, which allowed achieving
reaction yields of up to 94% (Nakazaki et al., 1981).
In addition to the diamantane synthesis based on more or
less easily available precursors, there have also been attempts to
synthesize diamantane in a stepwise fashion using the next smaller
diamondoid—adamantane—as a precursor. Using this approach,
diamantane could be synthesized from adamantane in several steps
126 Approaches for the Organic Synthesis of Diamondoids

that involved the functionalization of the adamantane structure

and subsequent ring closures and rearrangements (Farcasiu et al.,
1977). In principle, this approach could be extended to achieve the
synthesis of higher diamondoids, but because of the many reaction
steps involved, it has turned out to be not very practical.

6.2.3 Synthesis of Triamantane

As for the synthesis of adamantane and diamantane, for triamantane,
over the years many different reaction mechanisms have been
investigated. The most common methods that give the highest
reaction yields are summarized in Figs. 6.5 and 6.6. Also for
triamantane, the reaction yields highly depend on the nature of the
available precursors and catalysts.

a
CH2I2,
Zn(Cu)

H2, Pd, CH3

AlBr3,
2500 psi (17.2 MPa)
H 3C t-BuBr
2−5%

b
1. ClCOCOCl,
O
C 6H 6
COOH CH2N
2. CH2N2

3. CuSO4, Pt, H4,

toluene, ∆ 430ºC
4. EtMgBr 30%
5. C6H6, I2

Figure 6.5 Possible reactions for the synthesis of triamantane. (a) Use of
a cyclooctatetraene dimer as precursor. (b) With 1-diamantanecarboxylic
acid as a starting material. The percentage values indicate the reaction
yields and the symbol  indicates the use of heat. Adapted from
Schwertfeger et al. (2008).
 Conventional Organic Chemical Synthesis of Diamondoids 127

a
Pt, N2
+
250ºC

1. Butadiene
2. H2, Pt

3. AlCl3, ∆, 60%

b
[Cat]
+

Cat:
1) B(OSO2CF3)3, Freon-113; 70%
2) CF3SO3H-SbF5 (1:1); 71% Freon-113; 70%
3) CF3SO3H-B(OSO2CF3)3 (1:1); 69% Freon-113; 70%
c
[Cat]
+
Cat:
NaBH4 / CF3SO3H,
Freon-113; 92%

Figure 6.6 Possible reactions for the synthesis of triamantane. (a) With
Binor-S as a precursor. (b) Via rearrangement of heptacyclooctadecane. (c)
With heptacyclooctadecane and superacids as catalyst. The percentages
indicate the reaction yields and  symbolizes the use of heat. Adapted
from Schwertfeger et al. (2008).

The most common approach consists in the elaboration of

an isomer of triamantane (C18 H24 ), whose structure consists of
seven rings and which is then rearranged to yield the triamantane
structure. One example for the synthesis of triamantane consisted
in the use of a cyclooctatetraene dimer (Fig. 6.5a). An alternative
approach consists in the use of 1-diamantanecarboxylic acid as a
128 Approaches for the Organic Synthesis of Diamondoids

starting material, whose reaction scheme is depicted in Fig. 6.5b

(Burns et al., 1975). This method gave a reaction yield up to 30%.
Another synthetic route for the fabrication of triamantane
consists in the use of S-Binor as a precursor, as depicted in
Fig. 6.6a, which gave yields of up to 60% (Hamilton et al., 1976;
Hollowood et al., 1980). It has also been demonstrated that
triamantane can be obtained via catalysis of the rearrangement
of heptacyclooctadecanes in the presence of superacids (Farooq
et al., 1988). This approach is illustrated in the reaction scheme
of Fig. 6.6b. To achieve the synthesis, different types of catalysts
were used (labeled methods 1–3), which resulted in reaction yields
of up to 70%. Finally, it was also shown that triamantane can
be synthesized from heptacyclooctadecanes using NaBH4 /CF3 SO3 H
superacids as catalyst in a Freon-113 solution (Olah et al., 1989) (cf.
Fig. 6.6c).

6.2.4 Synthesis of Tetramantane

In addition to the lower diamondoids adamantane, diamantane, and
triamantane, extensive attempts were done to synthesize higher
diamondoids, starting with tetramantane. However, although many
groups were active in this field, up to now, only one structural isomer
of tetramantane, [121]tetramantane (also called antitetramantane),
has been synthesized. Figure 6.7 shows the synthesis steps for
obtaining antitetramantane (Burns et al., 1978), which is based on
the use of 1,6-diamantanedicarboxylic acid as a precursor. As for
triamantane, the synthesis of tetramantane has also been attempted
by using a solid catalyst-mediated rearrangement, namely on
platinum (Burns et al., 1975, 1976), which gave reaction yields of
up to 10%.
After the unsuccessful attempts to extend the approaches of
lower diamondoid synthesis, research on diamondoids waned in
the 1980s. Renewed interest in diamondoids only started after the
discovery of higher diamondoids up to undecamantane in natural
oil and gas reservoirs (Dahl et al., 2003a) at the beginning of
the 2000s.
 Limitations of the Organic Synthesis of Diamondoids 129

1. ClCOCOCl, ∆
2. CH2N2
HOOC
COOH 3. CuSO4,
+
toluene, ∆
4. EtMgBr
5. C6H6, I2

H2, Pt
–
–
350ºC
10%

Figure 6.7 Schematic of the reaction pathway of [121]tetraman-

tane (anti-tetramantane). The synthesis is based on the use of 1,6-
diamantanedicarboxylic acid as a starting material.

6.3 Limitations of the Organic Synthesis of

Diamondoids
To fabricate diamondoids—especially those with a large number
of cages, that is, n > 4—available in larger quantities (at least
grams), it is necessary to develop methods that allow synthesizing
and functionalizing diamondoids more effectively than present
methods. One approach that has shown to be promising is by both
discharge and electric discharge plasmas generated in supercritical
fluids. In the following section, we discuss the generation of pulsed
laser plasmas in supercritical fluids and their application for the
fabrication of nanomaterials, especially diamondoids.
The main reasons for the unsuccessful attempts for the synthesis
by conventional organic synthesis are mainly:

(1) A lack of adequate precursors and catalysts

(2) The fact that with increasing number of diamondoids, the pos-
sible number of reaction pathways and reaction intermediates
increases exponentially

Moreover, reaction intermediates can be trapped in local energy

minima, preventing further continuation of reactions that could lead
130 Approaches for the Organic Synthesis of Diamondoids

-18.4 -22.7 -21.8 -21.7

-11.9

-19.6
-18.0 -23.1
-19.6 -25.4
-25.2

-16.2 -17.3
-18.5
-23.3

-27.4 -25.4
-26.2
-16.0 -25.5
-13.5
-25.7
-26.4
-21.4
-29.5 -25.7
-28.3
-26.5

-22.2
-26.1
-18.0 -20.6

-20.2 -26.1
-27.7
-26.7 -21.0
-27.7
-20.0 -26.2
-25.5
-24.6

-29.6 -18.5 -28.7 -21.8

CH3
CH3

Figure 6.8 Possible reaction pathways for the synthesis of 2- and 1-

methyladamantane. The figure illustrates the complexity of synthesizing
diamondoids via organic synthesis. The values are indicate the standard
enthalpy of formation (H f0 ) in kcal.mol−1 . Adapted from McKervey (1980).

to the formation of a diamondoid. As an example, Fig. 6.8 displays

the different reaction schemes that are possible in the synthesis of 2-
and 1-methyladamantane.
 PART III

NOVEL APPROACHES FOR THE SYNTHESIS

OF DIAMONDOIDS BY MICROPLASMAS
Chapter 7

Diamondoid Synthesis by Electric

Discharge Microplasmas in Supercritical
Fluids

7.1 Introduction
In the previous chapters, we have presented a brief overview on
the formation of diamondoids in natural oil and gas reservoirs and
also given a summary of the different approaches to synthesize
diamondoids by organic chemistry. Because of the difficulty in
appropriate precursors and the increasing number of possible
reaction pathways, in practice the organic synthesis of diamondoids
with cage number n ≥ 4 are not practical and so far, there have been
no reports on the synthesis of diamondoids beyond tetramantane.
In this and the following chapters, we give an overview of
alternative diamondoid synthesis approaches. Namely, we introduce
the synthesis of diamondoids based on microplasmas, that is,
using electric discharge and pulsed laser plasmas generated in
supercritical fluids (SCFs) and at atmospheric pressure. Since the
results presented in this and the following two chapters are based
on our own work, the experimental approaches and results are

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
134 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

SCF Plasma
Ionized
Neutral
al cluster
cluster
ter
p Supercritical
Liquid fluid (SCF)
Solid

Critical point Cluster

pc Electron
Molecule
Triple
Gaseous plasma
point Radical Electron

Gas
Tc T

Ion Molecule

Figure 7.1 Phase diagram of a pure substance showing the different phases
of a pure substance and the critical point. Compared to conventional
gaseous plasmas, plasma in SCFs are expected to contain novel excited
species, that is, cluster ions and cluster radicals, that are expected to
enhance chemical reactions.

described in more detail compared to the previous chapters. In this

chapter, we will first briefly summarize the main properties of SCFs
and also present a few applications for chemistry and materials
processing.
SCFs are media in a state of temperature and pressure (T , p)
above the liquid–vapor critical point (CP), that is, where T ≥ Tcrit
and p ≥ pcrit . At such conditions, the liquid and gaseous phases
are not distinct anymore, and without lowering the temperature, the
liquid phase cannot be obtained by simply compressing the fluid.
This is illustrated in Fig. 7.1, which shows the phase diagram and the
molecular structure of a pure substance in the different phases, solid,
liquid, gaseous, and supercritical. Therefore, from a macroscopic
point of view, SCFs represent an intermediate state between liquids
and gases. As such, SCFs possess high density, high diffusivity, high
solubility, and low surface tension (Jessop and Leitner, 1999). In
 Introduction 135

Room
o temperature
p *H2O

20

15
p (MPa)

NH3

10
SO3 Methanol
SO2 CS2
CH4 Kr *CO2
O2 Ethanol
F2 *Xe Acetylene Cl2 Acetonitrile
Ethane Benzene
5 *Ar CCl4
Acetone
*N2 Toluene
Ne SF6 EA Cyclohexane
CF4
CO Propane TMS
H2 Octane
*He Isobutane Hexane
Heptane
0
0 200 400 600
T (K)
ρcrit
m

0.5 1.0 1.5 2.0 (×10-2 mol cm-3)

Figure 7.2 Position of critical points in relation to room temperature

(between 20◦ C and 26◦ C), indicated by the vertical line. TMS, tetram-
ethylsilane; EA, ethyl acetate. The color scale of the points indicates the
molar critical density, ρcrit
m
, between 0.2 and 2.4 × e − 2 mol.cm−3 . The
∗ symbol marks substances inside which electric discharge plasmas have
been generated in the SCF phase. Critical constants taken from Ambrose
et al. (2014).

addition, their properties e.g. density, heat capacity, and dielectric

constant, can be varied continuously by changing the pressure or
temperature, or both.
Figure 7.2 displays the critical values (temperature, Tcrit and
pressure, pcrit ) of various pure substances in relation to room
temperature (i.e., between 20◦ C and 26◦ C), and the color scale of the
CPs indicates the levels of the critical molar density, ρcrit
m
. The two
extremes of Tcrit and pcrit are represented by He (Tcrit = 5.2K , pcrit =
0.227 MPa), and H2 O (Tcrit = 647.2 K, pcrit = 22.06 MPa). The figure
also indicates the fluids that have been used for generating electric
136 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

Table 7.1 Comparison of average physical and transport properties of

liquid, SCF, and gaseous states. Most of the thermophysical properties of
SCFs are intermediate between those of gases and liquids. However, there
are also properties that are higher compared to liquids and gases in SCFs.
For example, the thermal conductivity κ reaches a maximum near the critical
point

Property Liquid SCF Gas

−3
Density (kg.m ) 600–1600 200–900 0.6–2.0
Viscosity (×105 kg.m−1 .s−1 ) 20–300 1–9 1–3
Diffusion coefficient (×108 m2 .s−1 ) 0.02–0.2 1–40 1000–4000
Thermal conductivity (×103 W.m−1 .K−1 ) 80 20–250 4–30
Surface tension (dyne.cm−1 ) 20–450 0 0

discharge plasmas. So far, electric discharges have been generated

inside the SCF phases of He, Ar, N2 , Xe, CO2 , and H2 O (marked by ∗
in Fig. 7.2).
Table 7.1 summarizes typical properties of liquid, supercritical,
and gaseous phases. As mentioned briefly in Section 9.1 and as
shown in the table, the properties of SCFs lie between those of
liquids and gases.
While many properties of SCFs are intermediate between those
of liquids and gases, this is not true in all cases. In the vicinity
of the critical point, the thermal conductivity, specific heat, and
compressibility attain a maximum, their values being significantly
higher compared to the respective values of the gaseous or liquid
states (Chen et al., 1999; Pittman et al., 1982; Vesovic et al., 1990;
Walas, 1985).
These unique characteristics including the critical anomalies
near the CP derive from the microscopic fluid structure, that is,
molecular clustering of SCFs.
In the next section, we give a brief overview of the techniques
necessary to generate plasmas in high-pressure media and SCFs.

7.2 Generation of Plasmas in Supercritical Fluids

The creation of plasma reaction fields in SCFs can be achieved
both by electric discharges and pulsed laser ablation plasmas,
 Generation of Plasmas in Supercritical Fluids 137

thereby combining the high reactivity of plasmas with SCF-specific

characteristics. In order to enable to use of plasmas in SCFs for
other applications such as materials processing the control of and
suppression of the gas temperature rise due to plasma generation is
of great importance.
A more general overview of SCFs, the history of their discovery,
experimental equipment, their main properties and applications for
chemical engineering is given in the book of Jessop (Jessop and
Leitner, 1999). In addition to this work, detailed descriptions of the
molecular properties of SCFs have also been compiled in a separate
monograph (Arai et al., 2001).
To generate electric discharges in SCFs, a high voltage (typically
a few hundred volts to a few kilovolts) has to be applied between
two electrodes. Applied voltage can either be a direct current (DC)
or alternating current (AC).
So far, different types of electric discharges have been generated
in high-pressure and supercritical fluids. For example, the genera-
tion of dielectric barrier discharge (DBD) plasmas in supercritical
argon (in the pressure range between 2 to 4.9 MPa) and using at
radio frequencies has been demonstrated (Suga et al., 2010). DBDs
where at least one electrode is covered by a dielectric and effectively
acts as a current limiter are sustained by the repeated formation
of streamers, which evolve on the order of nanoseconds (Raizer,
1991). The use of DBDs has permitted the generation, even under
high pressure, of nonequilibrium, low-temperature plasmas where
the temperature increase is inhibited (Becker et al., 2004; Iza et al.,
2008; Kogelschatz, 2007; Xu, 2001).
In this section, we introduce research related to the generation of
alternating current (AC) DBDs, that facilitated the generation of low-
temperature plasmas under high-pressure, including supercritical,
conditions. As has been briefly mentioned in the introduction, there
are many different possible configurations of DBD electrodes. In
the case of high-pressure and supercritical conditions, besides a
small gap distance between electrodes, an increase in the electric
field, for instance by using a very pointed electrode, permits to
reduce the breakdown voltage. Figure 7.3a shows a schematic of a
needle-type electrode that was used for generating DBDs in high-
pressure and supercritical conditions (Tomai et al., 2006). As high-
138 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

a b
Power supply
Tungsten needle
Discharge
Dielectric barrier
100 μm
Ground electrode

c Fixation clip d Top electrode

connection
TEM grid (Mo)
Spacer,
holder

e Ground
Ground electrode 6 mm
electrode connection
Substrate
e f
Top electrode
(TEM grid)
Clip g Ag paste
t

Ground
Substrate electrode 6 mm

Figure 7.3 Schematics and photographs of DBD electrodes during gener-

ation. (a, b) Needle-type DBD (Kikuchi et al., 2008; Tomai et al., 2006).
(c–f) Schematics of the electrodes and photographs of arrayed mesh-type
electrode. Parts of the figure are adapted from Tomai et al. (2007) and Stauss
et al. (2010).

voltage electrodes, the authors used Tungsten (W) needles with

outer diameters of 250 μm that were fabricated by electrochemical
etching. Soda-lime glass slides with thicknesses of 120–170 μm and
whose back surfaces had been coated with silver paste, were used as
ground electrodes. The authors generated plasmas in scCO2 , scN2 ,
scAr and scXe by applying a high AC voltage (frequency: 3 kHz;
voltage: 10.5 kVp-p ) to the W needles. This electrode configuration
enabled the realization of stable discharges with durations of over
an hour (Kikuchi et al., 2008; Tomai et al., 2006).
 Generation of Plasmas in Supercritical Fluids 139

Typical parameters of such DBD plasmas generated using the

needle electrode geometry shown in Fig. 7.3a are summarized
in Table 7.2. Current–voltage waveform measurements indicated
that streamers with durations of approximately 2 ns are generated
repeatedly from a few to several tens of times per cycle. While the
ionization degree in these streamers is on the order of 8×10−4 , close
to that of streamers in atmospheric-pressure DBDs (10−4 –10−3 ), the
high neutral density of the SCF leads to the formation of plasmas
with high electron densities of nel ≈ 5 × 1018 cm−3 .
Compared to a typical low-temperature plasma, the electron
density is more than 1000 times higher. Consequently, they can be
considered to be a class of particularly reactive plasmas (Tomai et al.,
2006, 2007).
However, in order to increase the quantities of materials
synthesized, it is necessary to enlarge the size of the plasma.
One way to achieve this and without sacrificing the small gap
distance is to array a number of smaller discharges. To that end,
micromachined DBD electrodes have been developed (Stauss et al.,
2010). The authors used commercially available TEM molybdenum
mesh grids, which served as high-voltage electrodes. Machinable
ceramic, serving as both a holder for the TEM grids and as
dielectric barriers, were used, a schematic of the electrode geometry
being shown in Fig. 7.3c. By arranging the TEM grids into a two-
dimensional array, large-area-gap electrodes with a surface area
of about 85 mm2 could be realized. A photograph of such a large-
area DBD generated in scXe is shown in Fig. 7.3f. In addition to
the size, which in principle could be extended to even larger sizes,
the advantage of using micromachined electrodes in comparison
to the needle electrodes is a better control of the gap distance.
With this type of electrodes, the authors succeed in obtaining stable
discharges for durations of up to three hours (Stauss et al., 2010).
In another study, radio-frequency (RF) plasmas in scCO2
were generated using a high-frequency torch at 27.12 MHz and
input powers of 30 W, using electrodes with a gap distance of
1 mm (Kawashima et al., 2007). These RF plasmas using a point-to-
point electrode geometry were used for the synthesis of tungsten
oxide nanowires.
140 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

Table 7.2 Typical experimental conditions for

needle-type DBD generated in SCF conditions (Tomai
et al., 2006, 2007)

Condition Value
Duration 2 ns
Streamer radius < 100 μm
Repetition rate Several to several tens / cycle
Peak current 0.1–1 mA
Current density 1.3–13 A.cm−2
Charge density > 5 × 1018 cm−3
Ionization degree > 8 × 10−4

Table 7.3 Comparison of experimental conditions for SCF plasma and

conventional SCF processes used for synthesizing CNTs

Condition SCF plasma synthesis SCF synthesis

Environmental temperature 304.2 1273 (Motiei et al., 2001)
(K) 823 (Lou et al., 2003)
Environmental pressure 7.4 1000 (Motiei et al., 2001)
(MPa) 70 (Lou et al., 2003)
Catalyst — Mg (Motiei et al., 2001)
Li (Lou et al., 2003)

The characteristics of the DBD plasma generated using the

needle electrode shown in Fig. 7.3a are summarized in Table 7.2, and
Table 7.3 lists the differences in the processing parameters between
a plasma generated in an SCF and conventional processes for the
synthesis of CNTs.

7.3 Electric Discharges in High-Pressure and

Supercritical Fluid Microreactors
The generation of electric discharges in high-pressure and super-
critical environments is not very straightforward, the high-pressure
(and high-temperature) conditions making it necessary to use
specialized reactor vessels adapted to such harsh conditions. From
the point of view of electric discharges generated in high-pressure
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 141

and supercritical media, an alternative approach, which relies on the

use of microreactor systems, has been proposed.
In fact, microfluidic reactor systems have shown promise
as alternative approaches to large-scale batch reactors, both in
analytical chemistry and materials synthesis (McMullen and Jensen,
2010). The small volumes of microreactors allow faster mixing
and more rapid heat exchange, which can lead to higher reaction
yields (Hartman and Jensen, 2009), enabling the realization of
ultrafast reactions (Yoshida et al., 2008), and giving unprecedented
control over chemical reactions (Mason et al., 2007). In addition,
they allow for more flexibility, improved safety, and less chemical
waste (Mason et al., 2007). Continuous flow operation also brings
about higher reproducibility and allows more accurate control
of reaction times and particle sizes by adjusting the residence
time (Marre and Jensen, 2010). Because of the small reaction
volumes involved, microreactors can also be operated under
conditions that are not easily achievable with large-scale reactors:
high temperatures (Tiggelaar et al., 2005) and pressures (Verboom,
2009), or even using SCFs (Marre et al., 2010, 2008; Trachsel et al.,
2009).
However, despite the advantages of microreactors over
macroscale reactors, the parameters that can be changed remain
limited to pressure, temperature, the concentrations of the reactants
and their flow rates.
In the following, we briefly present the approach that has
been adopted for the synthesis of diamondoids using electric
discharges generated inside microscale reactors at high-pressure
and supercritical conditions.
Figure 7.4a shows a schematic of the experimental setup (Oshima
et al., 2012). The reactor consisted of fused silica capillaries with
nominal inner and outer diameters of 700 ± 10 and 850 ± 20 μm,
respectively, which served as fluidic channels and dielectric barriers.
The electrode geometry consists of two electrodes separated by the
dielectric barrier. In this case, the outer, ground electrode consisted
of an indium tin oxide (ITO) thin film. The high-voltage electrode
consisted of a tungsten filament (nominal diameter of 500 μm),
which was inserted into the capillary.
142 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

As has already been mentioned, in the case of discharges

generated in high-pressure and supercritical fluids, it is essential
to control the conditions of the fluid—temperature and pressure.
For the microcapillary reactors, the fluid temperature was adjusted
by enclosing the capillary, and by adjusting the temperature of this
shield, at temperatures of 279.2–284.8 K, which corresponds to
the range of T /Tcrit = 0.964–0.983 for xenon (Tcrit = 289.75 K,
pcrit = 5.84 MPa). The temperature was monitored using a thermo-
couple attached to the capillary.
Here too, small amount of adamantane (24.8 ± 0.4 mg were
introduced into the fluid to serve as a precursor, before introducing
pressurized xenon (5.83–5.99 MPa; p/ pcrit = 0.998–1.026) into the
cell. For adjusting the pressure values, syringe pumps are often used,
because they allow to control the pressure and at the same also
enable achieving flow rates compatible with microreactor systems.
In this special case, the continuous-flow-mode operation of the
syringe pump, flow rates of 0.05, 0.1, and 0.5 ml min−1 were realized,
for which the reaction times were 100, 50, and 10 min, respectively.
The discharges were generated using sinusoidal HV signal. To
generate the plasma, a sine signal wave with a frequency of
10 kHz and a voltage of 3.95–6.02 kVp-p (peak-to-peak) was applied
(Fig. 7.4a). The detailed experimental conditions to generate the
electric discharges are summarized in Table 7.4.
Gas chromatography–mass spectrometry (GC-MS) measure-
ments were performed for further analysis of the collected material.
The power consumption of these types of discharge was found
to be of the order of orders of 100 mW to 1 W (depending on the
experimental setup, that is, the length of the electrodes and the gap
distance of the inner electrode, the power consumption can vary).
Raman spectra acquired on solid particles indicated that the
products were a mixture of sp2 - and sp3 -hybridized carbon
nanomaterials, including diamondoids.
GC-MS measurements were conducted with the following three
goals: 1) to estimate the amount of synthesized diamantane by
integrating the peaks determined in SIM mode, 2) to determine the
types of higher diamondoids that may have been synthesized, and
3) to investigate the presence of intermediate products in order to
determine possible reaction mechanisms.
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 143

a
TI PI Adamantane reservoir
Inlet
High-pressure fitting

TI
High-pressure
Xe pump Microcapillary
C
Condensation meas ITO film
Gas loop
cylinder Cooling / heating
circuit
Voltage probe PI

Function
generator HV amplifier
Outlet

W filament
Current HV probe
probe
Collection trap

Oscilloscope

b c Capillary Viewport

Fused silica microcapillary

Cooling / heating 20 mm
ITO film
Tungsten
filament
AC voltage 20 mm

Figure 7.4 Schematic of experimental setup of high-pressure plasma

microreactor. (a) Process flow diagram. The cooling loop is used to
liquefy/solidify xenon gas and the high-pressure pump is used to control the
flow rate. The pressure and temperature of the microreactor system were
monitored using pressure and temperature indicators (PI, TI), respectively.
The precursor, adamantane, was dissolved in a high-pressure cell (inner
volume 3 mL) and then flowed through the reactor. I –V and Q–V
curves were acquired concurrently using current and high-voltage probes
connected to an oscilloscope. For Q–V measurements, a capacitor, C meas , was
used. (b) Detailed view of electrode geometry. The electrode consists of a
fused silica capillary coated with ITO and a tungsten wire inserted into the
capillary. (c) Photograph of experimental setup (top) prior to and (bottom)
during plasma generation ( p = 5.90 MPa, T = 290.9 K, f = 10 kHz, Vappl =
4.6 kVp-p ). The three viewports at the top of the cooling/heating circuit allow
optical access to the capillary and the verification of plasma generation.
Figure adapted from Oshima et al. (2014).
144 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

Table 7.4 Experimental conditions for diamondoid synthesis using

microcapillary reactor (Oshima et al., 2014). For both batch and
continuous-flow approaches, the applied frequency was f = 10 kHz

Parameter Condition
Batch type
Temperature (◦ C) (T /Tcrit ) 15.6–16.5 (0.997–0.999)
Pressure (MPa) ( p/ pcrit ) 5.89–5.99 (1.009–1.023)
Applied voltage (peak-to-peak; kVp-p ) 4.32–4.78
Reaction time (min) 15–240
Adamantane (mg) 24.5–25.1
Flow type
Temperature (◦ C) (T /Tcrit ) 15.6–16.5 (0.997–0.999)
Pressure (MPa) ( p/ pcrit ) 5.83–5.96 (0.998–1.021)
Gas flow rate (mL min−1 ) 0.01, 0.05c , 0.1b , 0.5a
Peak-to-peak applied voltage (kVp-p ) 3.95–6.02
Reaction time flow (min) 10a , 50b , 100c
Adamantane (mg) 25.1–25.2
a
Flow rate of 0.05 mL/min.
b
Flow rate of 0.1 mL/min.
c
Flow rate of 0.5 mL/min.
Flow rates and respective reaction times correspond to residence times of tres = 4.2, 21,
and 42 s, respectively.

To begin with, we investigated the synthesis of diamantane

(n = 2, C14 H20 , relative molecular mass Mr = 188). The SIM spectrum
of a cyclohexane solution containing commercially available diaman-
tane (purity > 98.0%; Tokyo Chemical Industry) with a mass-to-
charge ratio (m/z) of 188 exhibited large peaks at a GC retention
time of tret = 8.3 min.
The SIM spectra for products with m/z 188 showed peaks at
the same GC retention time as the standard sample containing
diamantane. Moreover, the mass spectra of the products and the
standard sample at this retention time of 8.3 min exhibited similar
tendencies (Fig. 7.5). The large peak at m/z 188 was attributed
to the molecular ion of diamantane, and the smaller peaks at
the same m/z value and intensity ratio in both spectra at lower
m/z values corresponded to fragment ion peaks. On the basis of
the agreement of the retention time and mass spectrum of the
synthesized products with those of the standard sample, it is
concluded that the synthesized products contain diamantane.
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 145

a 100
Product M+•
188
80
Relative intensity (%)

60

40
91 131
20 79
159
105 117 145
67
53 173
0
b 100
Standard M+•
188
80
Relative intensity (%)

60

40
91
79 131
20 105 117
53 67 145 159
173
0
50 100 150 200
m/z

Figure 7.5 Typical mass spectra of diamantane. (a) Product synthesized in

the microcapillary microplasma reactor. (b) Mass spectrum of a standard
sample containing diamantane. The inset shows the molecular structure of
diamantane (for clarity, hydrogen terminations are not shown). Both mass
spectra were acquired at a retention time of tret = 8.3 min. Further, both
have a molecular ion peak at m/z 188, and the structure and intensity of
the fragment ion peaks of both spectra are in very good agreement. Data
adapted from Oshima et al. (2014).

The quantities of diamantane were evaluated by integrating the

m/z 188 SIM peak area near the retention time of 8.3 min. The area
intensities were then compared with those of a calibration curve
obtained by linear regression of the peak intensities measured for
standard diamantane solutions with known concentrations between
10 and 1 × 104 μg L−1 . The maximum quantity of synthesized
diamantane was found to be about ∼15 μg, and the yield for the
batch experiments was found to be ∼600 ppm.
146 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

a Group n 1 2 3 4 5 6 7 8 9 10 11
1 C4n+6H4n+12 136 188 240 292 344 396 448 500 552 604 656
2 C4n+5H4n+10 330 382 434 486 538 590 642
3 C4n+2H4n+6 342 394 446 498 550 602
4 C4n+4H4n+8 420 472 524 576 628
5 C4n+1H4n+4 432 484 534 588
6 C4n-2H4n 444 496 548
7 C4n-5H4n-4 456 508

b Group n 1 2 3 4 5 6 7 8 9 10 11
1 C4n+6H4n+12 136 188 240 292 344 396 448 500 552 604 656
2 C4n+5H4n+10 330 382 434 486 538 590 642
3 C4n+2H4n+6 342 394 446 498 550 602
4 C4n+4H4n+8 420 472 524 576 628
5 C4n+1H4n+4 432 484 534 588
6 C4n-2H4n 444 496 548
7 C4n-5H4n-4 456 508

c Group n 1 2 3 4 5 6 7 8 9 10 11
1 C4n+6H4n+12 136 188 240 292 344 396 448 500 552 604 656
2 C4n+5H4n+10 330 382 434 486 538 590 642
3 C4n+2H4n+6 342 394 446 498 550 602
4 C4n+4H4n+8 420 472 524 576 628
5 C4n+1H4n+4 432 484 534 588
6 C4n-2H4n 444 496 548
7 C4n-5H4n-4 456 508

d Group n 1 2 3 4 5 6 7 8 9 10 11
1 C4n+6H4n+12 136 188 240 292 344 396 448 500 552 604 656
2 C4n+5H4n+10 330 382 434 486 538 590 642
3 C4n+2H4n+6 342 394 446 498 550 602
4 C4n+4H4n+8 420 472 524 576 628
5 C4n+1H4n+4 432 484 534 588
6 C4n-2H4n 444 496 548
7 C4n-5H4n-4 456 508

Batch 0.5 mL min-1 0.1 mL min-1 0.05 mL min-1

Isolated from crude oil MW > 600

Figure 7.6 Relative molecular masses (Mr ) of possibly synthesized diamon-

doids. Columns with n = 1–11 indicate the number of diamondoid cages,
while rows indicate the diamondoid group. Shaded cells containing num-
bers in bold indicate diamondoids detected in the GC-MS measurements.
(a) Batch type, (b) continuous-flow experiment with flow rates of 0.5, (c)
0.1, and (d) 0.05 mL min−1 (cf. experimental conditions listed in Table 7.4).
Entries with orange borders correspond to diamondoids reported to have
been isolated from crude oil. Cells shaded in gray in the table indicate
diamondoids with Mr > 600; these were not investigated but are listed for
completeness. Data adapted from Oshima et al. (2014).
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 147

In addition to the GC-MS spectrum of diamantane, the spectra of

other diamondoids with n > 2 were also analyzed. Figures 7.6a–
7.6d show a list of diamondoids with Mr values below 600. The
columns indicate the order or cage number (n) of the diamondoids,
while the rows (1–7) indicate the diamondoid group.
The easiest way to increase the order of a given diamondoid
is to add an isobutyl framework (four carbon atoms and four
hydrogen atoms) to any plane consisting of a cyclohexane ring in
the diamondoids. This addition increases Mr by 52. For diamondoids
belonging to the first group, Mr increases with 136 + 52 (n − 1).
On the other hand, by suitably sharing cyclohexane planes with
other cages, smaller hydrocarbon units can be added to increase
the order of the diamondoids. For example, C3 H2 units are required
to produce pentamantane with Mr = 330 from tetramantane
(Mr = 292). The molecules on the far left in the second to seventh
groups are base molecules that are obtained by adding small units
to lower diamondoids, and a new cage is then grown on the left by
adding C4 H4 units.
The synthesis of triamantane and higher diamondoids was
examined on the basis of other GC-MS selected ion monitoring (SIM)
mode spectra. Because these diamondoids are not commercially
available, it was not possible to directly compare their retention time
and mass spectra with those of standard samples, as was done in the
case of diamantane. However, it has been reported that the GC-MS
spectra of diamondoids have two characteristics, both the retention
time and mass spectra (Balaban et al., 2007; Wingert, 1992). First,
the retention times of diamondoids increase almost linearly with
the relative molecular mass, while those of alkylated diamondoids
do not lie on a straight line.
Second, the mass spectra of higher diamondoids are nearly
featureless except for strong molecular ion base peaks and peaks
at M+ /2, which correspond to divalent molecular ions. On the basis
of these features, it was determined that higher diamondoids were
synthesized when the following three criteria were satisfied: (i) the
SIM spectrum had a peak whose signal-to-noise (S/N) ratio was
more than three; (ii) the retention time for the peak could be roughly
fit on a straight line; and (iii) the mass spectrum for the retention
time had a local maximum at a value that directly corresponded
148 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

100

80
Relative intensity (%)

60
394
M+•
40

20

0
50 100 150 200 250 300 350 400
m/z

Figure 7.7 Mass spectrum of a possibly synthesized heptamantane. For this

diamondoid, the number of cages is n = 7 and the relative molecular mass
is Mr = 394. Data adapted from Oshima et al. (2014).

to a possible relative molecular mass of a diamondoid (as listed in

Fig. 7.6). Finally, spectra that contained any peaks at m/z values
higher than the expected Mr values of the diamondoids were not
taken into account.
As an example, Fig. 7.7 shows a mass spectrum at a GC retention
time of 22.4 min that might correspond to heptamantane (n = 7,
C30 H34 , Mr = 394). Figure 7.6 lists the Mr values of diamondoids
that may have been detected in this study. For comparison, the figure
also indicates diamondoids reported to have been isolated from
crude oil (Dahl et al., 2003a,b), which are the entries in Fig. 7.6a–d
surrounded by orange borders.
In the batch-type experiment (cf. Fig. 7.6a), the possibly
synthesized diamondoids (except diamantane) were triamantane
(n = 3, C18 H24 , Mr = 240), one pentamantane (n = 5, C26 H28 ,
Mr = 344), one heptamantane (n = 7, C30 H34 , Mr = 394), two
octamantanes (n = 8, C34 H38 , Mr = 446 and C36 H40 , Mr = 472),
and two nonamantanes (n = 9, C38 H42 , Mr = 498 and C40 H44 ,
Mr = 524). Assuming that the order of diamondoids increases in
steps of one inside SCF plasmas, it is peculiar that tetramantane and
hexamantane were not detected.
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 149

One possible reason for this might be the difference in the

dissociation energy of the diamondoids. The energy associated
with the dissociation of diamondoids into lower diamondoids
and hydrocarbon fragments has been calculated from ab initio
simulations (Lu et al., 2005). Arranging these energies in the order
of increasing n, those of hexamantane (n = 6) and heptamantane
(n = 7) show local energy maxima.
It is expected that reactions in SCF plasmas will proceed not
only in a direction that leads to higher diamondoids but also in the
opposite direction, resulting in their dissociation and the formation
of lower diamondoids. This means that only energetically stable
diamondoids can survive in the reaction field. For example, most
of the tetramantanes that did not grow into pentamantanes were
found to dissociate back into triamantane, while pentamantanes
were unlikely to form tetramantanes. Another observation that can
be made regarding the types of possibly synthesized diamondoids
is that they belong to the first, third, and fourth groups (rows in
Fig. 7.6), whereas diamondoids belonging to the second group were
not observed. In the case of pentamantane belonging to the second
group (n = 5, C25 H30 , Mr = 330), two hydrogen atoms are close
to each other, leading to high steric hindrance (Balaban et al., 2007).
Furthermore, the maximum solid angle between the carbon bonds in
the cage structure of this pentamantane is more than 5◦ larger than
that of adamantane, which is free from any strain.
The extraction of this specific pentamantane and other dia-
mondoids in the second row from crude oil has not been
reported (Dahl et al., 2003a), which means that they are unstable
and unlikely to form via thermal equilibrium reactions. Moreover,
these diamondoids were not observed in the batch-type reactions
conducted in the present study. The types of possibly synthesized
diamondoids in the three experiments conducted at different flow
rates are summarized in Fig. 7.6b–d.
In the experiment with a flow rate of 0.5 mL.min−1 summarized
in Fig. 7.6b, diamantane (n = 2, C14 H20 , Mr = 188), triamantane
(n = 3, C18 H24 , Mr = 240), two pentamantanes (n = 5, C26 H28 ,
Mr = 344, C25 H30 , Mr = 330), and one heptamantane (n = 7,
C30 H34 , Mr = 394) may have been synthesized. For a flow rate of
0.01 mL.min−1 (Fig. 7.6c), the GC-MS analysis showed the presence
150 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

of diamantane (n = 2, C14 H20 , Mr = 188) and possibly triamantane

(n = 3, C18 H24 , Mr = 240), two pentamantanes (n = 5, C26 H28 ,
Mr = 344, C25 H30 , Mr = 330), one hexamantane (n = 6, C29 H34 ,
Mr = 382), one heptamantane (n = 7, C30 H34 , Mr = 394), two
octamantanes (n = 8, C34 H38 , Mr = 446 and C36 H40 , Mr = 472),
one nonamantane (n = 9, C34 H36 , Mr = 444), and one decamantane
(n = 10, C35 H36 , Mr = 456).
Finally, for the experiment conducted at a flow rate of
0.05 mL min−1 (Fig. 7.6d), the GC-MS analysis showed the presence
of diamantane (n = 2, C14 H20 , Mr = 188), and the possible synthesis
of triamantane (n = 3, C18 H24 , Mr = 240), two pentamantanes
(n = 5, C26 H28 , Mr = 344, C25 H30 , Mr = 330), one heptamantane
(n = 7, C30 H34 , Mr = 394), one nonamantane (n = 9, C41 H46 ,
Mr = 538), and one decamantane (n = 10, C42 H46 , Mr = 550).
These results show three tendencies. First, in all experiments,
pentamantane (C26 H28 , Mr = 344) belonging to the first group and
heptamantane (C30 H34 , Mr = 394) belonging to the third group
were synthesized, both of which have relatively high dissociation
energies (Lu et al., 2005).
This result supports the theory that the growth and dissociation
of diamondoids occur simultaneously, and that stable diamondoids
are more likely to survive in the reaction field. Second, some
diamondoids belonging to the second group were synthesized in
the flow experiments: pentamantane (C25 H30 , Mr = 330), hexam-
antane (C29 H34 , Mr = 382), and nonamantane (C41 H46 , Mr = 538).
These diamondoids have steric hindrance and their isolation from
crude oil has not been reported (Dahl et al., 2003a,b). In addition,
they were not observed in the batch-type experiment conducted
in the present study. The minimum reaction time for the batch-
type experiments was 15 min, longer than the longest residence
time in the flow-type reactions (tres = 4.2, 21 and 42 s). It is
suggested that dissociation reactions, which lead to more stable
diamondoid structures, were inhibited by the rapid flow of the
products out of the plasma reaction zone; therefore, diamondoids
belonging to the second group were not dissociated. This indicates
that the highly nonequilibrium reaction zone of an SCF plasma
allows the synthesis of molecules that cannot be formed via thermal
equilibrium reactions.
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 151

Finally, as can be seen in Fig. 7.6b–d, diamondoids of increasingly

high molecular mass form with increasing residence time. Focusing
on diamondoids in the second group, only pentamantane (C25 H30 ,
Mr = 330) was observed in experiment the experiment with a flow
rate of 0.5 mL.min−1 , which had the shortest residence time (4.2s).
In contrast, pentamantane (C25 H30 , Mr = 330) and hexamantane
(C29 H34 , Mr = 382) were observed in the experiment with a flow
rate of 0.1 mL.min−1 (tres = 21 s). Moreover, pentamantane (C25 H30 ,
Mr = 330) and nonamantane (C41 H46 , Mr = 538) were observed in
the experiment with the longest residence time of 42 s (experiment
with a flow rate of 0.05 mL.min−1 ).
It appears that pentamantane (C25 H30 , Mr = 330) grows into
larger diamondoids belonging to the second group. The same trend
can also be observed for the diamondoids belonging to the third
group. Heptamantane (C30 H34 , Mr = 394) was observed in all the
experiments; octamantane (C34 H38 , Mr = 446) was obtained in
the experiment with a flow rate of 0.1 mL.min−1 ; and decamantane
(C42 H46 , Mr = 550) was detected in the experiment where a
flow rate of 0.05 mL.min−1 had been adapted. It seems natural
that longer residence times lead to the synthesis of diamondoids
with more cages. However, it is strange that specific diamondoids
belonging to one group were observed while those belonging to
other groups were not. For example, hexamantane, heptamantane,
and octamantane belonging to the second group were not observed
in the experiment with the highest flow rate, 0.5 mL.min−1 . One
possible reason for this is that such diamondoids might have been
produced with very low yields that were below the detection limit
of GC-MS and therefore were not detected.

7.3.1 Investigation of Possible Diamondoid Reaction

Paths by GC-MS Analysis of Intermediate Products
The molecular structure of adamantane suggests that the fusion
of two such units does not directly lead to the formation of
diamantane but to that of 1-(1-adamantyl)adamantane. To obtain
diamantane using adamantane as a starting material, smaller carbon
fragments have to be added to the adamantane framework. During
diamond film growth by plasma CVD, hydrocarbon radicals mainly
152 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

H H
1
8 2 C radical
9
7 10 3
H
5
6 4
(1) (3) (5) (7)

CH3

CH3 CH3

(2) (4) (6) (8)

Figure 7.8 Schematic of a possible reaction mechanism for the synthesis

of diamantane from adamantane. The subsequent repeated removal of
hydrogen and the addition of methyl groups from adamantane (1) led to the
formation of 2-methyladamantane (3), 2,4-dimethyladamantane (5), 2,4,9-
trimethyladamantane (7), and finally diamantane (8). Numbers 1–9 in (1)
indicate carbon sites for hydrogen removal and methyl attachment. Dots in
the intermediate structures (2), (4), and (6), and the hydrogen and methyl
radicals symbolize unpaired electrons.

consisting of a single carbon atom are thought to be the main

growth source (Harris, 1990). Moreover, it has been reported
that the PLA of C60 fullerene targets containing graphite leads
to the growth of larger fullerenes (Dunk et al., 2012). In that
report, the authors stated that the mechanism is closed network
growth, in which carbon atoms and C2 dimers are incorporated in
the fullerene network without any cleavage of the cage network.
Further, the synthesis of several higher diamondoids from lower
diamondoids by free-radical reactions has been reported (Dahl et al.,
2010). The authors proposed the repeated removal of hydrogen
atoms and the addition of methyl radicals to dangling bonds as a
possible mechanism. Figure 7.8 illustrates such a possible reaction
mechanism for the synthesis of diamantane from adamantane.
This type of reaction may also be valid in for the synthesis
of diamondoids using electric discharges in supercritical xenon.
To confirm this hypothesis, the presence of methyl derivatives of
diamondoids was investigated in the GC-MS scan mode. First, SIM
chromatograms for m/z 150, which corresponds to the relative
molecular mass of methyladamantane, exhibited peaks at a GC
retention time of 5.1 min. As shown in Fig. 7.9, the mass spectrum
acquired at 5.1 min (Fig. 7.9a) is in good agreement with that of
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 153

a 135
Intensity (arbitrary units) 25 000 Product at tret = 5.1 min

20 000
79
15 000 150

93
10 000 67 107

5000 53 121

0
b 10 000 135
2-Methyladamantane
(NIST database) 79
Intensity (arbitrary units)

8000
67 150
6000
93
41 107
4000
55
2000 53
121

0
c 10 000 150
Tricyclo[4.3.1.13,8]undecane
(NIST database)
Intensity (arbitrary units)

8000

6000
93 135
4000
79 107

67 111
2000
55 120
0
40 60 80 100 120 140 160
m/z

Figure 7.9 Mass spectra of synthesized products close to the retention time
of adamantane. (a) Mass spectrum acquired for tret = 5.1 min. (b) Reference
mass spectrum and molecular structure of 2-methyladamantane. (c) Ref-
erence mass spectrum of tricyclo[4.3.1.13,8]undecane (homoadamantane).
As can be seen in the molecular structure of homoadamantane, two of the
rings consist of six carbon atoms, while the other rings consist of seven. All
spectra have a molecular ion peak at m/z 150; however, the characteristic
fragment ion peaks and their respective intensities indicate the formation
of 2-methyladamantane. Data adapted from Oshima et al. (2014).
154 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

2-methyladamantane (NIST/EPA/NIH Mass Spectral Library (EI),

2012), which is presented in Fig. 7.9b.
On the other hand, the mass spectrum of homoadamantane,
whose relative molecular mass is 150 but which has one additional
carbon atom introduced into one of the cycles in the adamantane
cage, shows the highest intensity peak at m/z 150. The largest peak
at m/z 135 suggests that a methyl unit can easily dissociate from
the adamantane framework during the electron ionization process
in the mass spectrometer. This result suggests that the first step
in producing diamantane from adamantane is the substitution of a
hydrogen atom of adamantane by a methyl radical. However, from
GC-MS measurements alone, it is not possible to infer which carbon
atom, secondary or tertiary, loses its hydrogen atom.
The presence of dimethyl- and trimethyladamantanes, whose
relative molecular masses are 164 and 178, respectively, were also
investigated. The chromatograms contained peaks that correspond
to these m/z values, their mass spectra exhibiting molecular ion
peaks (Fig. 7.10) and larger peaks at m/z values 15 less than those
of the respective molecular ion peaks. Other possible derivatives
of adamantane with Mr values of 164 and 178 are ethyl- and
propyladamantanes, respectively. However, the mass spectra of
these two derivatives show peaks at m/z 135 (NIST/EPA/NIH Mass
Spectral Library (EI), 2012), because the ethyl and propyl groups are
easily dissociated from their bases by electron ionization. Therefore,
the observed spectra are more likely to be those of dimethyl- or
trimethyladamantane than ethyl- or propyladamantane.
On the basis of this GC-MS spectra analysis, it is suggested
that methyl-, dimethyl-, and trimethyladamantanes are interme-
diate products in the synthesis of diamantane from adamantane.
Considering the possible intermediate structures that appear
in the formation of diamantane, the sites of the two methyl
groups in dimethyladamantane must be 2 and 4, and those of
trimethyladamantane must be 2, 4, and 9 (cf. numbering in
structure (1) of Fig. 7.8). Experimentally, 1,3-dimethyladamantane
cannot be distinguished from 2,4-dimethyladamantane and 1,3,5-
trimethyladamantane from 2,4,9-trimethyladamantane by GC-MS.
It is reasonable to assume that many different types of methyl
derivatives of adamantane are formed in parallel, and only specific
 Electric Discharges in High-Pressure and Supercritical Fluid Microreactors 155

a Dimethyladamantane
20 000
149
Intensity (arbitrary units)

15 000

10 000
164

5000

0
b
70 000 Trimethyl-
adamantane 163
Intensity (arbitrary units)

60 000
50 000
40 000
30 000
178
20 000
10 000
0
50 100 150 200
m/z

Figure 7.10 Mass spectra of reaction intermediates produced during the

synthesis of diamantane. (a) Dimethyladamantane (Mr = 164) and (b)
trimethyladamantane (Mr = 178). Data adapted from Oshima et al. (2014).

derivatives grow into diamantane. Although these derivatives do

not lead to the formation of diamantane, mass spectra that
may correspond to tetramethyl and pentamethyladamantane were
observed. Moreover, mass spectra corresponding to six molecules,
namely, methyl, dimethyl, and trimethyl derivatives of diamantane
and triamantane, were also observed.
In summary, the proposed growth mechanism that leads to
the formation of diamantane in SCF plasmas consists of the
repetition of two processes: (1) the removal of hydrogen atoms
and (2) the addition of methyl radicals to dangling bonds. Because
the carbon source was limited to adamantane in this study, the
additional methyl radicals most likely formed by the decomposition
156 Diamondoid Synthesis by Electric Discharge Microplasmas in Supercritical Fluids

of adamantane in the plasma. In the cage closure reaction from

trimethyladamantane to diamantane, other species such as carbon
ions might have been formed (Tsuda et al., 1986).
To achieve higher reaction yields, the promotion of elementary
steps such as the control of the electron temperature to remove
dangling hydrogen bonds more effectively, and the addition of
hydrocarbon sources to produce more methyl radicals is considered
a promising strategy.
In this study, the GC-MS spectra were obtained from solutions
collected after the synthesis and some of the gaseous products
may have been lost because of evaporation. For completely under-
standing diamondoid growth and determining the species involved,
one effective approach might be to conduct online monitoring
of gaseous products by connecting the microreactor directly to
a mass spectrometer (Licklider et al., 1995). Moreover, ab initio
calculations may help in determining possible reaction pathways
and in establishing the positions of additional methyl groups.
Diamondoids were synthesized using an SCF plasma microreac-
tor; adamantane was used as the precursor in this synthesis. GC-MS
spectra indicated that diamondoids up to decamantane (n = 10) may
have been synthesized. On the basis of GC-MS spectra that corre-
sponded to intermediate products, it is suggested that diamondoids
grew sequentially by the substitution of hydrogen terminations with
methyl radicals. Factors related to the physicochemical properties of
the diamondoids, that is, dissociation energy, steric hindrance, and
residence time, are considered to control the types of synthesized
diamondoids. In future work, it might be possible to achieve the
selective growth of higher diamondoids by controlling the radical
supply to the diamondoid precursors, using various hydrocarbon
additives or a combination of photochemical and plasma activation.
Finally, the present approach of using microplasmas in high-
pressure and SCF microfluidic reactors may be a promising strategy
for the synthesis of other nanomaterials.
Chapter 8

Synthesis of Diamondoids by Pulsed

Laser Plasmas

Pulsed laser ablation (PLA) by plasmas that are generated by

irradiating a solid target has been used since the appearance of
Ruby lasers in the early 1960s. Because of its versatility, PLA has
attracted a lot of attention, and it has shown a high potential
for a wide range of materials processing: deposition of thin solid
films, nanocrystal growth, surface cleaning and the fabrication of
microelectronic devices.
Compared to PLA in vacuum or gaseous environments, the
interactions between a laser pulse and a solid target in a confining
liquid, solution, or high-pressure medium are more complex, and the
fundamental aspects of PLA of solid targets in such conditions is still
only poorly understood.
It is also important to note that the ablation mechanisms
causing a plasma plume are different for nanopulse and pico- or
femtosecond laser pulses. While the detailed mechanisms are still
not understood yet, in the case of nanosecond pulses, material
ejection is thought to be dominated by thermal processes (Ashfold
et al., 2004). In nanosecond lasers, there are three main stages that
lead to the formation of a plasma. Laser photons couple both with

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
158 Synthesis of Diamondoids by Pulsed Laser Plasmas

electrons and phonons of the target material. The photon–electron

coupling results in an immediate rise of the electron temperature,
leading to vaporization of the target.
In the case of ultrashort (i.e., pico- or femtosecond) laser pulses,
the plasma formation mechanism is different. It is generally a
nonequilibrium process and the heating, forming of the plasma
plume, and material ejection occur after the laser pulse (Saito et al.,
2002, 2003; Sakka et al., 2002a,b). Electrons are excited only to a few
or few tens of electron volts. Consequently, the lattice temperature
remains unchanged, the main amount of the laser pulse energy being
mainly absorbed in a thin layer close to the surface. Therefore it is
more the photon absorption depth instead of the thermal diffusion
depth that governs the heated volume (Ogale et al., 1987; Patil et al.,
1987).
Besides the generation of pulsed laser plasmas in vacuum, PLA
plasmas have recently found increased use in liquids, for both the
synthesis and functionalization of nanoparticles (Amendola and
Meneghetti, 2009). In addition to mainly metallic nanoparticles,
PLA in liquid water has also been used for the synthesis of
nanodiamonds (Amans et al., 2009). The nanodiamond particle
obtained in this fashion consisted of a diamond core with diameters
ranging from 5 to 15 nm, surrounded by a graphitic shell with
a thickness ranging between 3 and 4 nm. It was found that the
synthesis of nanodiamonds occurs in a very narrow temporal
window, at the early stages of plasma formation. The shockwave
duration was found to be roughly twice the pulse duration (∼10 ns),
during which the pressure inside the shockwave reached values
between 4.5 and 22.5 GPa. After the shockwave subdues, the
pressure values are too low for generating diamondoids and only sp2
carbon is formed.
Figure 8.1 illustrates the mechanisms leading to plasma forma-
tion by irradiation of a target by a pulsed laser source, the generation
of shockwaves inside the target and the fluid, and the formation
and collapse of a cavitation bubble. In previous work (Saitow and
Yamamura, 2009), the authors demonstrated that the size of metallic
nanoparticles could be adjusted by changing the properties of the
supercritical medium.
Using PLA of highly oriented pyrolytic graphite (HOPG), the
synthesis of diamondoids was investigated (Nakahara et al., 2011,
 Synthesis of Diamondoids by Pulsed Laser Plasmas 159

t<0 t = 0 – τpulse t = 10-12 – 10-10 s

Pulse penetration Absorption of Detachment of the
in liquid the laser pulse ablated material
Solution Laser Laser Plasma Laser
pulse pulse plume pulse

Target

Shockwaves
t = 10-10 – 10-7s t = 10-6 – 10-4 s t = 10-6 – 10-4 s
Expansion and quen– Expansion and collapse Slow growth and agglo–
ching of plasma plume of cavitation bubble meration of NMs
Plasma
Plasma NM NM
Cavitation Plasma
plume
plume nucleation bubble agglomeration
plume
growth
NM
growth

Figure 8.1 Mechanisms of plasma formation and material removal by

pulsed laser ablation. The different snapshots illustrate the formation of
the plasma and subsequent generation of a shockwave inside the target and
the fluid, followed by the growth and collapse of a cavitation bubble, and
nanomaterial (NM) nucleation, growth, and agglomeration.

2010). Xenon and CO2 are the two gases whose critical temperature
is close to room temperature. However, while dielectric barrier
discharges can be generated relatively easily in supercritical xenon
(scXe), the main disadvantage of Xe is its prohibitively high cost,
which is about 1000 times more expensive than other supercritical
fluid (SCF) media such as Ar and CO2 (Jessop and Leitner, 1999). This
makes Xe less attractive as a supercritical medium for both science
and industry.
On the other hand, scCO2 is one of the most widely used SCFs,
having already found application in various fields, as it has been
described in the brief introduction on SCFs above.
For generating plasmas in SCFs, the use of high-pressure cells
that can withstand the high pressure of SCF media is necessary.
One design of a high-pressure cell that was used for realizing
pulsed laser plasmas in liquids and SCFs is presented in Fig. 8.2.
160 Synthesis of Diamondoids by Pulsed Laser Plasmas

a
Mirror

2nd harmonic
pulsed laser (λ 532 nm)
Lens PI TI

Inlet
Outlet

Gas Liquefaction
cylinder loop

Target
Collection
trap
Heating/cooling circuit
b Outlet
Cooling
circuit inlet PI TI

Inlet Outlet
Outer cell

c Plasma Sapphire window

Inner cell
Outer cell
Cooling circuit
x-y stage

Figure 8.2 Experimental setup for realizing diamondoid synthesis by

pulsed laser ablation in scCO2 and scXe. (a) Schematic of the experimental
setup consisting of a stainless steel high-pressure cell, a cooling/heating
circuit, a compression loop for pressurizing the gas and pressure, and
temperature indicators (PI and TI). At the end of the experiment, the
chamber is purged and the synthesized materials collected in a trap
connected to the outlet. (b) Top view of the high-pressure cell and
cooling/heating circuit that allows us to adjust the temperature in the inner
cell. (c) Side view of the high-pressure cell. The pulsed laser light is focused
onto a target through a sapphire window and the high intensity of the laser
leads to rapid heating of a zone close to the laser spot and formation of the
plasma.
 Application of Pulsed Laser Plasmas in Supercritical Fluids to Nanomaterial Synthesis 161

The main part of the equipment consists of a stainless steel cell that
contains the pressurized gas. The temperature and the pressure in
the inner cell can be monitored by a thermocouple and pressure
sensor, respectively. The outer cell contains a water circuit that
allows us to control the temperature in the inner cell.
For condensing Xe and to reach SCF conditions, the gas is flown
through a liquefaction loop cooled by liquid nitrogen. In the case
of CO2 , the gas is usually compressed using a high-pressure pump.
The compressed gas is then introduced into the cell. After the
experiment, the synthesized materials are collected in a liquid trap
connected to the outlet of the high-pressure cell.

8.1 Application of Pulsed Laser Plasmas in

Supercritical Fluids to Nanomaterial
Synthesis
Figure 8.3 shows a series of shadowgraph images that were acquired
near the critical point of CO2 . The images show the variation of the
fluid after the irradiation by the laser pulse. At a delay of 3 μs after
the irradiation, one can observe the formation of a shockwave. Then,
after about 17 μs, one can observe the formation of transparent shell.
This double structure is only observed for conditions close to the
critical point.
In contrast to PLA in liquids, PLA in SCFs has not been used
as much up to now. One example of PLA is the fabrication of
gold nanoparticles by PLA in scCO2 (Saitow and Yamamura, 2009).
In addition to noble metal nanoparticles, the same group also
investigated the formation of silicon nanocrystals (Si-nc) by PLA of
Si targets. They could show that the size and crystal structure of
the Si-nc (core vs. shell) could be changed by adjusting the density
of the SCF medium. Close to the critical point, the cooling rate is
maximum.
Sasaki et al. (Sasaki and Aoki, 2008) investigated the effect
of the pressure of the supercritical medium on the formation of
nanoparticles.
162 Synthesis of Diamondoids by Pulsed Laser Plasmas

1 µs 3 µs 5 µs 7 µs 10 µs
Plasma Shockwave Cavitation
Bubble

Laser
Ni Target

15 µs 16 µs 17 µs 20 µs 30 µs

“Innerࠉ
Bubble”
50 µs 100 µs 250 µs 350 µs 600 µs

2 mm

Figure 8.3 Series of shadowgraph images acquired in liquid CO2 . The

conditions of the fluid were close to the critical point (T = 302.0 K,
p = 7.30 MPa). Between 7 and 17 μs, the cavitation bubble displays a
particular structure that consists of an inner bubble and an outer, partly
transparent shell. Images adapted from Urabe et al. (2013).

8.2 Synthesis of Diamondoids by Pulsed Laser

Plasmas
In the following, we describe the application of PLA in supercritical
CO2 (scCO2 ) for the synthesis of diamondoids (Nakahara et al.,
2011, 2010). The authors used a 3 mL high-pressure cell (see
Fig. 8.2c), and a highly oriented pyrolitic graphite (HOPG) target,
which was placed in a batch-type high-pressure cell (inner volume:
3 cm3 ). Adamantane (purity >99.0%) was dissolved in scCO2 with
and without cyclohexane as a co-solvent; see the experimental
conditions listed in Table 8.1.
The high-density CO2 was realized by condensation of the
CO2 gas (purity > 99.995%) in a liquefaction loop cooled by
liquid nitrogen before introducing it into the inner cell. A second-
 Micro-Raman Spectroscopy 163

Table 8.1 Experimental conditions for PLA in scCO2 with and without
cyclohexane adopted in the study of Nakahara et al. (2011)

Parameter scCO2 scCO2 with cyclohexane

−2
Adamantane concentration (1.2–12) × 10 (3.1–6.2) × 10−2
(mol L−1 )
Cyclohexane concentration – 7.7 × 10−1
(mol L−1 )
Temperature T (K) 304.5–305.2 304.5–304.8
Reduced temperature (T /Tcrit ) 1.001–1.004 1.001–1.002
Pressure p (MPa) 7.42–7.59 7.54–7.56
Reduced pressure ( p/ pcrit ) 1.005–1.028 1.022–1.024

harmonic neodymium-doped yttrium aluminum garnet (Nd:YAG)

laser (λ = 532 nm) was used for the ablation of the HOPG targets in
both scXe (Nakahara et al., 2010) and scCO2 . The maximum energy
was 7 mJ per pulse, giving a maximum fluence of approximately
18 J.cm−2 on the surface of the HOPG target. The pulse width was
7 ns, with a repetition rate of 10 Hz. The ablation experiments were
conducted for periods of 60 min. The synthesized products were
retrieved by evacuating the gas through a collection trap containing
10 mL of cyclohexane.

8.3 Micro-Raman Spectroscopy

Figure 8.4 is a collection of Raman spectra of products isolated after
PLA in scCO2 with and without cyclohexane as a cosolvent (both
before and after pyrolysis) (Nakahara et al., 2011), together with the
Raman spectrum of the material obtained by PLA in scXe (Nakahara
et al., 2010).
For illustrating the effect of increasing cage numbers on the
Raman spectra, in Fig. 8.4f,g the spectra of commercial adamantane,
and [12312] hexamantane (Filik et al., 2006b) are also included.
The Raman spectra of the products obtained by PLA in scCO2 ,
regardless of the presence of cyclohexane, presented almost the
same features that are known to be characteristics of Raman
spectra of diamondoids, that is, well-resolved peaks in the range
164 Synthesis of Diamondoids by Pulsed Laser Plasmas

CH wag / CH2 twist

CCC breathing / deformation CH2 scissors CHx stretch

a scCO2 before pyrolysis

b scCO2 after pyrolysis

c scCO2 / cyclohexane before pyrolysis

Intensity (arb. unit)

d scCO2 / cyclohexane after pyrolysis

e scXe before pyrolysis

f Adamantane

g [12312] hexamantane

400 600 800 1000 1200 1400 1600 2800 3000

Raman shift (cm-1)

Figure 8.4 Micro-Raman spectra of synthesized products obtained by PLA

and compared to spectra obtained on diamondoids isolated from crude oil.
(a) Products synthesized in scCO2 before pyrolysis. (b) Spectrum obtained
on products after pyrolysis. (c) In scCO2 with cyclohexane before pyrolysis.
(d) After pyrolysis. (e) In scXe before pyrolysis (Nakahara et al., 2011). For
illustrating the effect of increasing cage number, the Raman spectra of (f)
commercial adamantane and (g) [12312]hexamantane (Filik et al., 2006b)
are included as examples. (f) The three strongest Raman active vibration
modes for adamantane, corresponding to C−C breathing, CH wag/CH2 twist,
and CHx stretching modes, respectively, are also indicated. Data adapted
from Nakahara et al. (2011).
 Micro-Raman Spectroscopy 165

1000–1500 cm−1 and strong peaks in the high-energy region,

2800–2950 cm−1 .
On the other hand, the peaks in the measured Raman spectra
are supposed to originate from a mixture of different hydrocarbons.
Moreover, it is known that the Raman scattering signal varies largely
for each material, for example, sp2 -hybridized carbon shows a
much stronger Raman signal compared to that of sp3 -hybridized
carbon (Ballutaud et al., 2008; Wada et al., 1980). Therefore, it
is possible that the peaks from synthesized diamondoids and
those from other hydrocarbons such as paraffin and aromatics
get balanced out, which could explain the lack of strong peaks
in the low-energy region below 500 cm−1 . The features in the
wavenumber range between 1000–1500 cm−1 and the peaks in
the range between 2800–2950 cm−1 , which are characteristic of
sp3 CHx stretching modes (Ballutaud et al., 2008), indicate the
presence of diamond-structured hydrocarbons in the synthesized
products. The existence of diamond-structured hydrocarbons in the
synthesized products was also indicated for PLA in scCO2 , both
with and without cyclohexane. In all the Raman spectra of the
synthesized materials, no indication of the precursor adamantane
could be found. This is attributed to the fact that adamantane
sublimes even at room temperature and that for increasing
the concentration of the samples, the solutions collected after PLA
were evaporated. Interestingly, the Raman spectra collected from the
products obtained by PLA in scCO2 with and without cyclohexane
showed similar characteristics. Thus, even when cyclohexane was
added as a cosolvent, the synthesized materials, which possess
relatively high Raman scattering cross sections, seemed to be almost
identical for the products obtained by PLA in neat scCO2 . Smaller
differences that are found in the Raman spectra for the samples
obtained in scCO2 which cyclohexane as a cosolvent are attributed to
the possible synthesis of additional species which could be formed
by the dissociation of cyclohexane. In contrast, the differences
between the products obtained by PLA in scCO2 and scXe (Nakahara
et al., 2010) were bigger. For example, the strongest intensities in the
low-energy region (300–1500 cm−1 ) appeared around 1440 cm−1
for PLA in scCO2 with and without cyclohexane, while the most
166 Synthesis of Diamondoids by Pulsed Laser Plasmas

intense Raman peaks appeared around 1050 cm−1 for PLA in scXe.
Moreover, the shapes of the strong peaks in the high-energy region
(2800–3000 cm−1 ) vary considerably. These dissimilarities indicate
that the synthesized materials were different for PLA in scCO2
and scXe. The effect of pyrolysis for the samples obtained by PLA
in scCO2 and in scCO2 /cyclohexane are shown in Figs. 8.4a,b and
8.4c,d, respectively. Compared to the spectra before pyrolysis, the
biggest difference can be observed in the high-wavenumber region
between 2980 and 3000 cm−1 . The intensity of the peaks that are
attributed to sp2 CHx stretching modes (Ballutaud et al., 2008) were
lower after pyrolysis. In addition, the peaks in the high-wavenumber
region become better resolved. From this we conclude that pyrolysis
permitted to reduce the number of nondiamondoid hydrocarbons.
However, we assume nondiamondoid hydrocarbons to persist in the
samples even after pyrolysis and that more separation steps are
necessary to separate diamondoids from nondiamondoids.

8.4 Gas Chromatography–Mass Spectrometry

8.4.1 Synthesis of Diamantane
The retention times for m/z 136 and m/z 188, which correspond to
the molecular weights (MWs) of adamantane and diamantane (n =
2), respectively, were compared for products obtained by PLA in
scCO2 with and without cyclohexane, and the standard solution with
dissolved commercial adamantane and diamantane. The standard
sample was prepared by dissolving both commercially available
adamantane and diamantane (purity >98.0%) in cyclohexane, each
with a concentration of 5.0 mg.L−1 . The comparison revealed the
same time lag, 3.5 min, for all experimental conditions. Moreover, the
mass spectra of the gas chromatography–mass spectrometry (GC-
MS) measurements at the retention times of selected ion monitoring
(SIM) for m/z 188 for both products from PLA in scCO2 with and
without cyclohexane presented almost the same fragments as those
of the standard diamantane; see Fig. 8.5.
From this data, it can be concluded that diamantane was
synthesized. To estimate the production rate of diamantane, a
 Gas Chromatography–Mass Spectrometry 167

a scCO2 M+•
188
Ion abundance (arb. unit)

b scCO2 with cyclohexane

c Diamantane

50 100 150 200

m/z

Figure 8.5 GC-MS mass spectra acquired at a retention time of t = 7.3 min.
(a) Synthesized product obtained in neat scCO2 . (b) Product synthesized in
scCO2 and cyclohexane. (c) Mass spectrum of diamantane of the standard
sample. The inset shows the molecular structure of diamantane. The main
feature of the mass spectra is the molecular ion peak at m/z 188 and
fragment peaks that are characteristic of diamantane. Data adapted from
Nakahara et al. (2011).

calibration curve was constructed. For this, cyclohexane solutions

with diamantane concentrations of 0.0, 1.0, 2.0, 4.0, and 10.0 mg.L−1
were prepared. Figure 8.6 shows the comparison of the SIM
peak areas as a function of the concentration of diamantane. By
comparing the SIM peak areas of the synthesized products, the
production rate of diamantane was estimated to be 0.2 μgh−1 for
PLA in both scCO2 with and without cyclohexane; see Table 8.2.

8.4.2 Possible Synthesis of Diamondoids with n ≥ 3

SIM curves and mass spectra indicated the possible synthesis of
diamondoids consisting of three or more cages by PLA in scCO2 . At
first, however, only triamantane (n = 3) was observed in addition to
168 Synthesis of Diamondoids by Pulsed Laser Plasmas

Table 8.2 SIM peak area and estimated diamantane concentration of the
product obtained by PLA in scCO2

Supercritical Diamantane
medium for Solution for SIM peak area concentration
PLA GC-MS analyses (arb. unit) (mg L−1 )
scCO2 Sample in 1 mL cyclohexane 2100 0.23
scCO2 w. Sample in 1 mL cyclohexane 1900 0.21
cyclohexane

Data adapted from Nakahara et al. (2011).

110000
100000
90000
SIM peak area (arb. unit)

80000
70000
60000
50000
40000
30000
20000
10000
0
0 1 2 3 4 5 6 7 8 9 10
Diamantane concentration (mg L-1)

Figure 8.6 Calibration curve fitted to the GC-MS SIM peak area correspond-
ing to m/z 188 with cyclohexane solution with dissolved diamantane. The
GC-MS scan rate was 1.79 scans.s−1 . Data adapted from Nakahara et al.
(2011).

diamantane for PLA in pure scCO2 . We suggest that this might be due
to the poor solubility of adamantane in scCO2 . To improve the signal-
to-noise ratio in the GC-MS measurements, the sample solution was
enriched by using a smaller amount of solvent (cyclohexane of 20 μl
instead of 1 mL). As a result, more peaks were observed that could
be attributed to diamondoids consisting of up to 12 cages. The cage
numbers of eluted diamondoids obtained by PLA in scCO2 with and
without cyclohexane as a function of the experimentally determined
GC-MS retention times are listed in Tables 8.3 and 8.4, and Fig. 8.7,
respectively.
 Gas Chromatography–Mass Spectrometry 169

Table 8.3 List of possibly synthesized diamondoids by PLA in scCO2 , with

their molecular formulae, MWs, GC-MS relative retention times, and dual
graph codes

Cage number Molecular M+ (m/z) GC-MS relative Structure

(n) formula base peak retention time
2 C14 H20 188 1.000 Diamantane
3 C18 H24 240 1.189 Triamantane
4 C22 H28 292 1.509 e.g., [121]
6 C29 H34 382 1.986 e.g., [12(1)31]
C30 H36 396 2.038 e.g., [12121]
7 C30 H34 394 1.843 e.g., [123121]
10 C35 H36 456 2.111 [1231241(2)3]
12 C45 H46 586 2.495 e.g., [12131431234]

Data adapted from Nakahara et al. (2011).

Table 8.4 List of possibly synthesized diamondoids by PLA in scCO2 with

cyclohexane as a cosolvent, with their molecular formulae, MWs, GC-MS
relative retention times, and dual graph codes

Cage number Molecular M+ (m/z) GC-MS relative Structure

(n) formula base peak retention time
2 C14 H20 188 1.000 Diamantane
3 C18 H24 240 1.188 Triamantane
4 C22 H28 292 1.510 e.g., [121]
6 C26 H30 342 1.627 [12312]
C29 H34 382 1.987 e.g., [12(1)31]
C30 H36 396 2.039 e.g., [12121]
8 C34 H38 446 2.156 e.g., [1213(1)21]
10 C45 H50 590 2.423 e.g., [12(3)1(2)3(1)23]
12 C45 H46 586 2.493 e.g., [12131431234]

Data adapted from Nakahara et al. (2011).

The relative retention times were calculated by dividing the

individual retention times by the retention time of diamantane in
the range 7.148–7.157 min. The GC-MS signals can be assigned to
the following diamondoids: triamantane at m/z 240; tetramantane
at m/z 292; hexamantanes at m/z 342, 382, and 396; heptamantane
at m/z 394; octamantane at m/z 446; decamantanes at m/z 456
(C45 H46 ) and 590; and dodecamantane at m/z 586. From Fig. 8.7
once can see that the GC-MS retention times increase almost linearly
170 Synthesis of Diamondoids by Pulsed Laser Plasmas

12 MW scCO2
590
586 scCO2 with cyclohexane
Number of cages (n)

10 456
446
396
8 394
382
342
6 292
240
188
4

1.0 1.5 2.0 2.5

Relative retention time

Figure 8.7 Variation of the number of diamondoid cages obtained by CO2

with and without cyclohexane as a function of the GC-MS relative retention
time. The retention time of diamantane (t = 7.148–7.157 min) is taken as
the reference retention time and the color map indicates the MW of the
detected diamondoids. Diamondoids with higher MWs need increasingly
longer elution times for being detected by MS, the increase being almost
linear. Data adapted from Nakahara et al. (2011).

with the number of cages, which is in agreement with previous

work (Balaban et al., 2007).
Furthermore, the relative retention times of the diamondoids
obtained by PLA in scCO2 both with and without cyclohexane
showed good agreement: triamantane (1.188–1.189); tetramantane
(1.509–1.510); hexamantanes (1.986–1.987 for a MW of 382 and
2.038–2.039 for a MW of 396); and dodecamantane (2.493–2.495).
In addition, some of the observed diamondoids, corresponding to
a MW of 382, 586, and 590, were not found in previous works in
which the diamondoids were isolated from petroleum (Dahl et al.,
2003a). These molecules were detected at high GC temperature,
higher than the maximum GC temperature used by another group
(593 K). For example, molecular ion peaks corresponding to a MW
of 586 appeared when the GC oven temperature was raised to 620 K.
In GC-MS measurements, each diamondoid is expected to elute at a
distinct retention time. In contrast, for higher diamondoids, there
are MW groups that have many structural isomers. For example,
MW 292 (tetramantane) has 4 possible isomers and MW 396
 Gas Chromatography–Mass Spectrometry 171

Ion abundance (arb. unit)

M+
M+/2 456
228

100 200 300 400 500 600

m/z

Figure 8.8 GC-MS mass spectrum of possible superadamantane (MW 456)

obtained by PLA in scCO2 . The inset shows the molecular structure of
superadamantane. Data adapted from Nakahara et al. (2011).

(hexamantane) has 28. Therefore, in the GC-MS measurements,

diamond molecules corresponding to the same MW group but
possessing different structures are expected to elute at different
retention times. However, each MW group of diamondoid had only
one or a few points per analysis in this study, even for those with
a large number of possible structural isomers. Considering the
relatively fast heating rate of GC-MS (20 K.min−1 ) and the slow scan
rate at 1.79 scans.s−1 compared to those of other groups (10 K.min−1
and 2.94 scans.s−1 ) (Dahl et al., 2003a), the resolution of the GC-MS
analyses was about 30% of the other groups’ analyses. Therefore,
it is expected that different isomers could appear at the same scan
times, even if they elute at different times. Slower heating rates
or faster scan rates will be used in future studies to improve the
resolution of GC-MS analyses. Figure 8.8 shows an example of mass
spectra corresponding to a MW of 456. The diamondoid corre-
sponding to MW 456 is the most compact decamantane (n = 10),
[1231241(2)3] decamantane, also known as superadamantane.
The spectrum shows a typical feature of unsubstituted higher
diamondoids, that is, a strong molecular ion peak M+ at m/z 456
with a few fragment ions including the M/2 +·
peak at m/z ≈ 228,
which corresponds to the doubly charged molecular ion. Strong
172 Synthesis of Diamondoids by Pulsed Laser Plasmas

peaks at low m/z in Fig. 8.8 are supposed to be due either to

other hydrocarbon molecules such as paraffin and aromatics that
co-elute at the same retention time, or to other materials that
originated from the GC column and the septum that appear in the
entire GC-MS analysis. The results of the GC-MS analyses can be
summarized as follows: (i) There were many possible diamondoids
synthesized, and their GC-MS retention times generally increase
with the number of cages; (ii) some of the synthesized diamondoids
have not been reported before, which might be due to the high GC
oven temperature of up to 633 K; (iii) all MW groups of diamondoids
had only one or a few points per analysis, which could be explained
by the lower scanning resolution of the GC-MS analyses; and (iv)
the mass spectra showed features that were similar to those of
previously reported diamondoids with high MW, that is, a large
molecular ion peak and a small number of fragment peaks.

8.4.3 Effects of Pyrolysis on Synthesized Products

The mass spectra acquired after the pyrolysis experiments and cor-
responding to possible higher diamondoids are listed in Tables 8.5
and 8.6.
The observed peaks were different before and after pyrolysis.
However, the molecular ion peak with a MW of 456 was observed
both before and after pyrolysis. Moreover, the relative retention

Table 8.5 List of observed higher diamondoids for

PLA in scCO2 after pyrolysis

Cage number Molecular M+ (m/z) GC-MS relative

(n) formula base peak retention time
5 C25 H30 330 1.70–2.25
5 C26 H32 344 2.30–2.31
7 C30 H34 394 2.02
7 C34 H40 448 2.45
9 C34 H36 444 1.66
9 C37 H40 484 2.20
10 C35 H36 456 2.12–2.13
10 C44 H48 576 2.57
 Comparison between PLA in scCO2 and scXe 173

Table 8.6 List of observed higher diamondoids for

PLA in scCO2 with cyclohexane after pyrolysis

Cage number Molecular M+ (m/z) GC-MS relative

(n) formula base peak retention time
4 C22 H28 292 1.34
5 C26 H32 344 1.83
6 C30 H36 396 1.67
7 C32 H36 420 2.01
7 C34 H40 448 2.45

Data adapted from Nakahara et al. (2011).

times of GC-MS were very close to each other. This result suggests
that the synthesized products with a MW of 456 survived after
pyrolysis. It is expected that nondiamondoid hydrocarbons of high
MW will decompose after thermal treatment at 723 K. Therefore,
the present results suggest that the peak corresponding to a MW
of 456 originated from superadamantane. Many MW groups of
diamondoids such as those with n = 5 and 7 cages, were not
found before pyrolysis, although they were found after the pyrolysis
experiments.
In scCO2 , species originating from the decomposition of CO2
could possibly participate in the formation of new materials.
Assuming those materials were nondiamondoid hydrocarbons and
were decomposed after pyrolysis, this might explain why the
observed spectra contained peaks corresponding to diamondoids
with five and seven cages only after pyrolysis.

8.5 Comparison between PLA in scCO2 and scXe

There are MW groups that were only synthesized in scXe and not
in scCO2 (Nakahara et al., 2010). Moreover, the production rate of
diamantane of PLA in scCO2 was 0.2 μgh−1 , which is lower than that
of PLA in scXe. This could be attributed to the lower solubility of
adamantane in scCO2 compared with that of scXe. The production
rate of diamantane is approximately the same in neat scCO2 and
in the scCO2 /cyclohexane mixture. Therefore, while the solubility
174 Synthesis of Diamondoids by Pulsed Laser Plasmas

of adamantane in scCO2 can be enhanced using cyclohexane as a

co-solvent, this is probably not the only factor for increasing the
production rate. In the case of scXe, the molecules of the medium
do not participate in the reaction, whereas in the case of scCO2 , CO2
itself can also dissociate and form reaction products. Consequently
it is suspected that the lower reaction yield of diamantane in scCO2
is due to both the lower solubility of adamantane and competing
reactions resulting in the formation of nondiamondoids. In contrast,
the mass spectrum showing a MW of 456 was only obtained by
PLA in pure scCO2 . C−C and C−H bonds must be dissociated to
allow the formation of successive diamondoids from adamantane.
In the previous work where diamondoids were synthesized by DBD
in scXe (Stauss et al., 2010), it was suggested that the absence of
oxidants resulted in a preferential dissociation of C−C bonds and
led to the synthesis of diamondoids with a high H/C ratio. On the
contrary, the products from PLA in scCO2 include relatively low
H/C ratio diamondoids compared with those in scXe. It is supposed
that oxidant species originating from scCO2 might lead to selective
dissociation of C−H bonds, enabling the synthesis of low H/C ratio
diamondoids, such as superadamantane.

8.6 Conclusions and Perspectives

In this chapter, we have reviewed diamondoids; their structure,
physical and chemical properties; and a short overview of their
current main and possible future applications. While smaller dia-
mondoids up to tetramantane can be synthesized by conventional
organic chemical methods, the synthesis beyond tetramantane has
turned out to be not possible.
PLA was performed in scCO2 with and without cyclohexane as a
cosolvent. Raman spectra of the synthesized products indicated the
presence of sp3 -hybridized materials including diamondoids. From
GC-MS measurements, this indicates the synthesis of diamantane
and possibly other, higher-order diamondoids, including those
with number of cages larger than reported so far (n = 12) and
superadamantane (n = 10). Because oxidant species originating
from scCO2 might lead to the selective dissociation of C−H bonds,
 Conclusions and Perspectives 175

synthesis of higher-order diamondoids, such as superadamantane,

could be realized. Moreover, the authors found that there were
more higher-order diamondoids with n = 5–10 for PLA in scCO2 .
In summary, PLA in SCFs and in particular scCO2 is considered
to be a promising approach for the synthesis of higher-order
diamondoids.
Chapter 9

Synthesis of Diamondoids by
Atmospheric-Pressure Microplasmas

This chapter addresses a more recent alternative approach for

the synthesis of diamondoids. As discussed in Chapters 7 and
8, both electric discharge and pulsed laser plasmas generated
in supercritical fluids (SCFs) allow the synthesis of diamondoids.
However, one disadvantage of the use of these types of plasmas is
the necessity to use specialized high-pressure equipment. In this
chapter, we introduce a recent alternative approach, which is based
on the use of microplasma reactors that are operated at atmospheric
pressure. After a brief review of atmospheric-pressure microplasma
sources, we give a short overview of the results.

9.1 Introduction
As has been shown in the previous chapters, the synthesis of
diamondoids is not straightforward, and the quantities that can be
realized are not sufficient for application in industry.
Specifically, we have shown that nanodiamonds (Kikuchi et al.,
2010) and diamondoids can be synthesized both by electric

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
178 Synthesis of Diamondoids by Atmospheric-Pressure Microplasmas

discharges (Shizuno et al., 2011; Stauss et al., 2010) and by pulsed

laser ablation plasmas in supercritical xenon (Nakahara et al., 2010)
and CO2 (Nakahara et al., 2011).
These previous studies were conducted using a batch-type
process, that is, the reactions are realized keeping the system closed
during the synthesis, without any in- or outflow. However, it has
been shown that often continuous-flow microreactors, where the
precursors are continuously introduced into the reactor, can yield
better reproducibility and higher reaction yields (Hartman and
Jensen, 2009). The reason is that in microfluidic reactors, thermal
control is easier compared to macroscale reactor systems. The first
combination of a microplasma and a high-pressure microfluidic
reactor was demonstrated recently (Oshima et al., 2012, 2014),
the system allowing increasing the reaction yields of diamondoids
compared to those of previously used macroreactors. However,
the realization of such high-pressure microplasma reactors is
not straightforward, which is mainly due to the specialized high-
pressure equipment and the high-pressure fittings.
On the other hand, the possibility of rapid, continuous gas-
phase growth of semiconductor nanowires has been demon-
strated (Heurlin et al., 2012), and the growth speed and morphology
were shown to be influenced by the flow rate and precursor
size. In addition, continuous-flow microplasma reactors operated at
atmospheric pressure have been used for the synthesis of metallic
nanoparticles (Chiang et al., 2010; Lin et al., 2012).
As an alternative to high-pressure microfluidic microplasmas,
an atmospheric-pressure continuous-flow process using dielectric
barrier discharge (DBD) plasma microreactors for the synthesis of
diamondoids was developed. In this system, again adamantane was
used as a precursor and seed, employing gases used in conventional
chemical vapor deposition (CVD) diamond growth (Bachmann
et al., 1991), that is, methane (CH3 ) and hydrogen (H2 ). In the
following sections, we will first give a brief overview of atmospheric-
pressure microplasma reactors that were used for the synthesis of
metallic nanoparticles and nanodiamonds, before introducing the
microreactor system used for the synthesis of diamondoids.
 Microchip Microplasma Reactors 179

a Function b
generator HV amplifier w Top
electrode
Outlet
Top electrode Quartz chip
d
Microchannels

Plasma Ground
Gas inlet 1 electrode

Gas inlet 2 Bottom

(ground)
electrode

Figure 9.1 Geometry of a microchip microplasma reactor and its cross

section. (a) Three-dimensional view of a quartz microreactor containing
20 microchannels. Gas inlets 1 and 2 were used for introducing the
different types of source gases, including the precursor adamantane, into
the microplasma reactor. (b) Cross section of a single micoreactor channel
with indium tin oxide (ITO) as the top electrode, and a grounded bottom
electrode. The channel widths w and depths d of the microplasma reactors
ranged from 400 to 500 μm, and 100 to 200 μm, respectively. Reprinted
from Ishii, C., Stauss, S., Kuribara, K., Urabe, K., Sasaki, T., and Terashima,
K. (2015). Atmospheric-pressure synthesis of diamondoids by plasmas
generated inside a microfluidic reactor, Diamond and Related Materials 59,
pp. 40–46, Copyright (2015), with permission from Elsevier.

9.2 Microchip Microplasma Reactors

Figure 9.1 displays the schematic experimental setup that was
employed for diamondoid synthesis using microplasma reactors.
Here, custom-made chip microreactors fabricated out of glass were
used that were realized by using lithography and powder blasting.
The top and bottom electrodes consisted of an indium tin oxide film
(to have optical access to the reactor), while the bottom electrode
consisted of silver.
To realize the glass microreactors, self-adhesive UV photosensi-
tive films and inkjet-printed transparency masks were used. This
allowed achieving fluidic channels with widths of 400 ± 50 μm and
depths of 250 ± 50 μm).
For the synthesis experiments, the microchip reactors were
fixed inside a custom-made compression holder similar to those
180 Synthesis of Diamondoids by Atmospheric-Pressure Microplasmas

developed for high-pressure microfluidic reactors (Marre et al.,

2010).
The temperature of the cylinder that contained the precursor
adamantane, the tubing system, and the microreactor was adjusted
using resistive heaters. Prior to each synthesis experiment and
before flowing the reactant gases into the cell, the system was
evacuated using a rotary pump. The temperature of the pipes
and the reactor and the pressure at the inlet of the reactor were
monitored using temperature and pressure indicators. The electric
discharges were generated by applying a sine wave signal produced
by a function generator and an alternating current (AC) high-voltage
amplifier.
The synthesis experiments were conducted for durations of
120 or 240 min at a frequency of f = 10 kHz, and applied peak-
to-peak voltages that varied between 3.2–4.3 kVp-p (cf. Table 9.1 for
the detailed experimental conditions). To investigate the influence
of the gas composition, in particular the addition of hydrogen (H2 )
and methane (CH4 ), on the synthesis of diamondoids, we used
four different gas mixtures: adamantane (Ada) vapor/1% CH4 /1%
H2 /argon (Ar), Ada/0.5% CH4 /Ar, Ada/1% H2 /Ar, and Ada/Ar.
The gas and the synthesized products were first flown through
a collection trap filled with cyclohexane, and then a solid-phase
extraction filter, to collect products that might not have been
retained by the cyclohexane trap.
After the synthesis, the tubes and the microreactor were flushed
by pumping cyclohexane through the whole system. The solid-
phase extraction filters were also flushed separately by pumping
cyclohexane through them and the solutions collected. To increase
the concentration of the products for analysis, the cyclohexane was
first evaporated on a hot plate at a temperature of 85◦ C before
adding 1 mL of cyclohexane to redissolve the products.
The collected samples were then characterized by gas chroma-
tography–mass spectrometry (GC-MS). In addition to the total
ion chromatograms (TICs), selected ion monitoring (SIM) chro-
matograms corresponding to molecular masses of diamondoids in
the mass-to-charge (m/z) range of 136–600, and those of possible
reaction intermediates up to m/z 300 were acquired. Individual
mass spectra were also measured in the scan mode over an
 Plasma Generation and Characterization 181

Table 9.1 Experimental conditions adopted for diamondoid

synthesis (Ishii et al., 2015). The concentration of the precursor
adamantane ρ is calculated from the expression of the sublima-
tion pressure of adamantane by Bazyleva et al. (2011), under
the assumption of a perfect gas. For a temperature of 300 K, the
adamantane sublimation pressure is 0.02 kPa, and at 320 K, it
is about 0.09 kPa (i.e. for both temperatures, the adamantane
content in the gas mixtures was below 0.1%). The residence time
of about 0.1 s was estimated from the fixed flow rate (20 sccm)
and the reactor geometry

Parameters Symbol Values

Argon Ar 92–100 %
Methane CH4 0–4 %
Hydrogen H2 0–4 %
Total flow rate Qtot 20 sccm
Residence time tres ∼0.1 s

Average temperature T 300, 320 K

Pressure p 100 kPa
Applied voltage Vappl 3.2 − 4.3 kVp-p
Applied frequency f 10 kHz
Adamantane concentration ρ ∼1.2, ∼4.7 g m−3
Plasma generation time tp 120, 240 min

m/z range of 40–1000. For the identification of possible reaction

intermediates, we compared the retention times of peaks in the TIC
and SIM data to those of diamondoids and derivates isolated from
crude oil (Liang et al., 2012) and by matching of the experimental
mass spectra to reference mass spectra (NIST/EPA/NIH Mass
Spectral Library (EI), 2012).
In addition to the analysis of the synthesized products by GC-
MS, the authors also monitored the plasmas by current–voltage
(I –V ) and charge–voltage (Q–V ) measurements and optical emis-
sion spectroscopy (OES).

9.3 Plasma Generation and Characterization

Figure 9.2 shows an example of a microreactor containing 20 paral-
lel microchannels with photographs prior to (Fig. 9.2a) and during
182 Synthesis of Diamondoids by Atmospheric-Pressure Microplasmas

a Top electrode connection b Inlet

10 mm 10 mm Outlet

Figure 9.2 Photographs of microplasma reactor during synthesis. (a) Top

view through ITO electrode of reactor prior to plasma generation. The
dotted lines indicate the geometries of the microchannels and the positions
of the inlet and outlet. (b) Photograph of reactor during plasma generation
(experimental conditions: T = 320 K; Vappl = 3.6–3.7 kVp-p ; f = 10 kHz).
Reprinted from Ishii, C., Stauss, S., Kuribara, K., Urabe, K., Sasaki, T., and
Terashima, K. (2015). Atmospheric-pressure synthesis of diamondoids by
plasmas generated inside a microfluidic reactor, Diamond and Related
Materials 59, pp. 40–46, Copyright (2015), with permission from Elsevier.

(Fig. 9.2b) plasma generation. The trapezoidal geometry of the inlet

and outlet zones, as indicated in the photograph in Fig. 9.2a, allow
one to achieve approximately the same gas velocity distribution in
all microchannels (Commenge et al., 2002).
The discharge current (Id ) was calculated from the measured
current (Im ) and applied voltage (Vappl ) curves (Stauss et al., 2013).
Typical capacitances for estimating Id were of the order of C g =
6 ± 2 pF (capacitance due to gas gap), C sd = 14 ± 3 pF (capacitance
of glass slides), and C p = 11 ± 2 pF (parasitic capacitance). In the
current–voltage waveforms, a broad current peak in the positive and
negative half-cycles appears, the (absolute) maximum current being
of the order of ∼2 mA. In this case, because of the very low current,
individual discharge peaks inside this broad discharge peak could
not be observed.
The power consumption for this discharge was found to be
P = 134 ± 1 mW.cm−2 .
In general, for the applied voltages used for the synthesis, the
average power consumption of the discharges was found to be in the
range of ∼130–200 mW.cm−2 . The variations are mainly attributed
 Plasma Generation and Characterization 183

to the different gas compositions and differences in the channel

depths.

9.3.1 Optical Emission Spectroscopy Measurements

Figure 9.3 shows optical emission spectra of the discharges
generated for four experimental conditions where the levels of H2
and CH4 were set to values between 0% and 1%, respectively.

a CH C2
Normalized intensity (arbitrary units)

Ar I Ar I

4 Ada / 1% CH4 / 1% H2 / Ar

3
Ada / 0.5% CH4 / Ar

2
Ada / 1% H2 / Ar
1

Ada / Ar
0
300 400 500 600 700 800 900 1000
Wavelength (nm)

b CH A 2Δ→X 2Π c C2 A 3Πg→X3Πu
30 30
Intensity (arb. units ×10 -2)

Intensity (arb. units ×10 -2)

25 25
20 20
15 15
10 10
5 5
0 0
420 425 430 435 440 505 510 515 520
Wavelength (nm) Wavelength (nm)

Figure 9.3 Optical emission spectra of four different experimental condi-

tions. (a) Overview in the wavelength range of 300–1000 nm. (b) CH A 2  →
X 2 band at 431.4 nm. (c) C2 A 3 g → X 3 u Swan band at 516.5 nm. The
detailed spectra in (b) and (c) were normalized with respect to the 811 nm
Ar I line. Data adapted from Stauss et al. (2014).
184 Synthesis of Diamondoids by Atmospheric-Pressure Microplasmas

The topmost spectrum (Fig. 9.3a) shows an overview of the

plasma emission in the wavelength range between 300 and 1000 nm
for the four experimental conditions indicated in the graph. The
most prominent peaks are due to argon neutral radicals (Ar I) in the
range of 680–850 nm.
To investigate the effect of the gas composition on the optical
emission spectra, CH and C2 bands and the atomic hydrogen lines at
486.1 (Hβ ) and 656.3 nm (Hα ) were monitored. Figure 9.3a shows a
detailed view of the CH A 2  → X 2 band at 431.4 nm and Fig. 9.3b
of the C2 A 3 g → X 3 u Swan band at 516.5 nm.
In the case of the Ada/Ar mixture, atomic H emission could not
be detected, whereas in all the other compositions, only the Hα line
could be observed, but its intensity was very weak. In a previous
study, OES measurements during the synthesis of diamond films
using direct current microplasma discharges at pressures between
100 and 500 torr (Sankaran and Giapis, 2002) did not show the
presence of C2 bands. However, the authors observed strong Hα and
Hβ emission. Here, as shown in Fig. 9.3b,c, when CH4 is added to the
gas, both CH and C2 bands were observed, which are attributed to
the dissociation of adamantane and CH4 . In the case of the Ada/1%
H2 /Ar mixture, the intensities of these two bands are very weak,
whereas for Ada/Ar, the intensity is higher. The reason could be
that in the absence of H2 , almost all of the plasma’s energy is used
primarily for the dissociation of adamantane.
It has been shown previously that in the growth of ultrananocrys-
talline diamond, C2 emission is stronger, whereas for the synthesis
of nanocrystalline diamond, CH bands are dominant. As will be
discussed later, the presence of CH and C2 can probably attributed
to both the dissociation of adamantane and CH4 . Therefore, for
achieving higher reaction yields, it might be advantageous to realize
plasma conditions where the adamantane cage is preserved and only
precursor gases that act as a carbon source are dissociated.
In addition, in conventional CVD growth of diamond, the
presence of atomic hydrogen is crucial (May et al., 2006). Therefore,
it is expected that higher H2 concentrations than those employed in
the studies of Stauss et al. (2014) and Ishii et al. (2015) could enable
more efficient diamondoid synthesis.
 Plasma Generation and Characterization 185

9.3.2 GC-MS Analysis of Diamantane and Reaction

Intermediates
Since OES does not allow quantitative analysis very easily, the
prediction of reaction mechanisms is difficult, if not impossible. Fur-
thermore, other species that are considered relevant for diamond
synthesis, such as CH3 and C2 H2 , are not observable in optical
emission (Williams et al., 2006). Therefore, in addition to OES mea-
surements and to understand the influence of the gas composition
on diamondoid synthesis, we have also investigated the presence of
possible reaction intermediates by GC-MS measurements.
Figure 9.4 shows mass spectra of the synthesized product and
a standard sample that contained a mixture of adamantane and
the second diamondoid, diamantane, both acquired at the same
retention time tret = 8.3 min. The sample (Fig. 9.4a) was synthesized
at conditions of T = 300 K, Vappl = 4.0 kVp-p , and f = 10 kHz, in a
mixture of Ada/4% CH4 /Ar.
The mass spectrum of the synthesized product and the one of
the standard sample (Fig. 9.4b) both contain a prominent peak at
m/z 188, which is the molecular ion peak of diamantane, which has
a relative molecular mass (Mr ) of 188. In addition to the acquisition
of the mass spectrum at the same retention time and the presence of
the molecular ion peak at m/z 188, both mass spectra have similar
fragmentation patterns (the smaller differences are attributed to the
lower quantity of the synthesized sample when compared to the
standard sample). This shows that diamantane can be synthesized
from adamantane by atmospheric-pressure microplasmas.
Figure 9.5 displays the TICs of products collected in the
cyclohexane trap and obtained using four different gas mixtures, for
retention times between 4.1 and 7.8 min, that is, before the elution
of diamantane (tret = 8.3 min).
The large broad peak at tret ≈ 3.9–4.1 min is due to the
precursor adamantane. At a retention time of about 3.3–3.4 min
in all gas mixtures, one can observe a prominent peak that is
ascribed to 1-methyladamantane (1-MA). For all gas compositions,
at tret ≈ 5.1 min, the TICs also contain a peak corresponding to 2-
methyladamantane (2-MA); however, this peak is most prominent
for the cases including CH4 (1% and 0.5%). Finally at tret ≈ 5.9 min,
186 Synthesis of Diamondoids by Atmospheric-Pressure Microplasmas

100 188
Product M+•
Relative intensity (%)

80

60
91
40 79
105
20 145 145 159 173
117

0
100 188
Standard M+•
Relative intensity (%)

80

60
79 91
40
55
67
20 105 131
117 145 159
173
0
50 100 150 200
m/z

Figure 9.4 Mass spectra of synthesized product and standard diamantane

sample. Both the product and reference sample were acquired at a retention
time tret = 8.3 min for an adamantane/4% CH4 /Ar plasma. (a) The spectrum
acquired of the synthesized product shows a base peak at m/z 188. (b)
The standard sample shows a mass spectrum that has the same dominant
peak at m/z 188, which is due to the molecular ion of diamantane (M +· ).
The fragment peaks and their distributions are also similar, which indicates
the synthesis of diamantane. Synthesis conditions: T = 300 K (adamantane
vapor pressure 0.02 kPa), Vappl = 4.0 kVp-p , f = 10 kHz, plasma generation
time tp = 240 min. Adapted from Stauss et al. (2014).

one can observe the appearance of a peak that can be attributed to

1,4-dimethyladamantane (1,4-DMA).
The integrated TIC peak intensities of the adamantane deriva-
tives, 1-MA, 2-MA, and 1,4-DMA, acquired for the four different gas
compositions are presented in Fig. 9.6. As can be seen in the graphs,
the quantities of the investigated adamantane derivatives, which
might play a crucial role as reaction intermediates in the synthesis
of diamantane from adamantane in one possible proposed step-wise
reaction mechanism (Oshima et al., 2014), highly depend on the
 Plasma Generation and Characterization 187

Ada 1-MA 2-MA 1,4-DMA

0.4
Normalized intensity (arb. units)

Ada / 1% CH4 / 1% H2 / Ar

0.3

Ada / 0.5% CH4 / Ar

0.2

Ada / 1% H2 / Ar
0.1

Ada / Ar
0.0
4.5 5.0 5.5 6.0 6.5 7.0 7.5
Retention time (min)

Figure 9.5 Total ion chromatograms of products synthesized for four differ-
ent gas mixtures. The shaded regions in the graph indicate respectively the
retention times of the precursor adamantane (Ada), 1-methyladamantane
(1-MA), 2-methyladamantane (2-MA), and 1,4-dimethyladamantane (1,4-
DMA). The corresponding molecular structures are also displayed on the
top of the graph. Data adapted from Stauss et al. (2014).

gas chemistry. In the case when only Ar is present in the gas, the
formation of reaction intermediates is very low. Consequently, for
achieving higher reaction yields, it is necessary to adjust the plasma
gas chemistry so that the two main intermediate reaction steps,
that is, hydrogen abstraction and addition of alkyls, can proceed
efficiently.
For the cases where no CH4 or H2 was added to the plasma
gas, the intensities of methyladamantanes are close to zero. In
addition, one can see that there is a competition in the formation
of 1-MA and 2-MA. Considering the structure of diamantane and its
formation starting from adamantane, 1-MA and similar derivatives,
that is, those that form by addition of alkyls at tertiary C-positions in
adamantane, are not desirable, because such molecular structures
do not allow the formation of the next higher diamondoid (Oshima
et al., 2014). However, the gas-phase enthalpy of formation is
−170 ± 1 kJ.mol−1 for 1-MA and -154 kJ.mol−1 for 2-MA (Clark et al.,
188 Synthesis of Diamondoids by Atmospheric-Pressure Microplasmas

Ada / 1% CH4 / 1% H2 / Ar
1,4-DMA
2-MA
1-MA

Ada / 0.5% CH4 / Ar

1,4-DMA
2-MA
1-MA

1,4-DMA Ada / 1% H2 / Ar

2-MA
1-MA

Ada / Ar
1,4-DMA
2-MA
1-MA

0 50 100 150 200 250

Intensity (arb. units)

Figure 9.6 Intensities of adamantane derivatives 1-methyladamantane

(1-MA), 2-methyladamantane (2-MA), and 1,4-dimethyladamantane (1,4-
DMA) for four different plasma gas compositions. The intensity values were
obtained by integration of the peak areas in the total ion chromatograms.
Data adapted from Stauss et al. (2014).

1979), and from ab initio calculations the ground-state energy of the

1 − adamantyl+ cation was found to be −10604.51 eV, which is more
stable compared to 2 − adamantyl+ (−10604.04 eV) (Steglich et al.,
2011).
In addition, in the case of the Ada/Ar mixture, the presence of CH
bands in the OES and the appearance of adamantane derivatives in
the GC-MS measurements indicate that the precursor adamantane
is dissociated by the discharge. The bonding energy of the (sp3 )C–
C(sp3 ) bonds in adamantane is weaker than the (sp3 )C−H bonds in
both adamantane (Shen et al., 1992) and CH4 , and consequently, the
dissociation of the C−C bonds by the plasma is more probable in
comparison to cleaving of the C−H bonds.
Therefore it is surmised that even when 2-MA is formed, it
might not persist in sufficient quantities to allow further hydrogen
 Summary 189

abstraction and subsequent carbon radical addition. Consequently,

assuming that one possible reaction mechanism of diamantane
growth from adamantane at atmospheric pressure consists of
repeated hydrogen abstraction and methyl attachment (Oshima
et al., 2014), conditions that promote the formation and persistence
of reaction intermediates, that is, 2-MA, 2,4-DMA, and 2,4,9-
trimethyladamantane have to be established.
The quantities of diamantane obtained in the present study
were of the order of a few nanograms, about 1 to 2 orders
of magnitude smaller than what was obtained by synthesis in
supercritical xenon, where the maximum quantity of diamantane
obtained was on the order of micrograms (Oshima et al., 2014).
One reason for the lower yields could be the lower concentration
of the precursor adamantane at atmospheric pressure: For the tem-
peratures employed in the present study, the estimated adamantane
concentrations were ∼1.2 and 4.7 g.m−3 , whereas for the plasma
microreactor using supercritical xenon near its critical point allowed
to dissolve adamantane of the order of ∼2000 g.m−3 . Furthermore,
it is surmised that in the case of plasmas generated in supercritical
conditions, the presence of high-density clusters containing ions or
neutral radicals aids in the reaction of diamondoids.

9.4 Summary
In this chapter, we have presented alternative approaches for the
synthesis of diamondoids, which are based on plasmas generated in
different gases with pressures ranging from atmospheric conditions
up to SCFs.
DBDs allowed us to synthesize diamantane using adamantane
as a precursor and seed. Similar to what has been observed in
liquid-based chemistry synthesis, it seems that when compared
to conventional batch-type reactors, the efficiency of reactions
can be enhanced by using microscale reactors. Investigation of
reaction mechanisms by GC-MS indicate that one possible reaction
mechanism consists in repeated hydrogen abstraction and addition
of methyl groups.
190 Synthesis of Diamondoids by Atmospheric-Pressure Microplasmas

We have also presented research on plasmas generated in SCFs

and their application to the synthesis of diamondoids. While much
easier to realize because there is no need to control the electrode
geometry, currently there are no easy means to scale up pulsed
laser ablation processes that would allow increasing the quantities
of diamondoids synthesized.
Finally, we have demonstrated the possibility of employing
DBD microfluidic reactors for the synthesis of diamondoids at
atmospheric pressure. One possible reaction mechanism of larger
diamondoids from adamantane is considered to take place in a
stepwise reaction that consists of repeated hydrogen abstraction
and addition of carbon-containing fragments such as alkyls. GC-MS
measurements showed that the formation of possible intermediates
highly depends on the gas composition, namely the presence of
species that can provide carbon to form next larger diamondoids.
The present results show that diamondoids can be synthesized at
atmospheric pressure, albeit in lower quantities than in previously
employed plasmas generated in high-pressure and supercritical
conditions. However, it is suggested that by adjusting the plasma
chemistry, higher reaction yields could be realized. It is also
surmised that by employing much higher frequencies (i.e., in the
ultrahigh frequency or microwave range) to generate the plasmas,
the quantities of synthesized products could be increased.
Compared to conventional organic chemistry synthesis, while
very promising, the approaches presented in this chapter are still in
their infancy. For further improving diamondoid synthesis by these
different, plasma-based processes, more in-depth characterization
of the products is necessary, not only after collection, but also during
synthesis. Therefore, online measurement of the plasma species by
MS might help to further advance the proposed synthesis process.
Chapter 10

Conclusions and Perspectives

With this chapter, we conclude our journey into the field of diamon-
doids. We started it by presenting the reader with an introduction
about diamondoids, their molecular structure, and their naming
conventions and also by introducing their main chemical and
physical properties, including their electronic structure and optical
and vibrational properties. We have also given a short overview
of their current and possible future applications, which span a
wide range of different scientific and technological fields: medicine,
pharmaceutics, biotechnology, materials science, and opto- and
nanoelectronics.
In addition, we have briefly talked about how diamondoids can
form in natural gas and oil reservoirs and the methods to isolate
and purify them. We have also discussed the currently known
approaches to obtaining diamondoids by conventional organic
chemical synthesis.
At the moment, only the two smallest diamondoids, adamantane
and diamantane, are available in quantities large enough (tons/year)
so that they can be used on an industrial scale. While higher diamon-
doids up to undecamantane have been found in oil reservoirs, their
availability is limited to research purposes only.

Diamondoids: Synthesis, Properties, and Applications

Sven Strauss and Kazuo Terashima
Copyright c 2017 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4745-18-5 (Hardcover), 978-1-315-36466-7 (eBook)
www.panstanford.com
192 Conclusions and Perspectives

On the basis of the current knowledge of the possibilities

of organic chemistry and the unsuccessful attempts to obtain
diamondoids beyond triamantane by these methods, it seems that
alternative synthesis approaches are desperately needed in order to
realize the fabrication of higher diamondoids in quantities useful for
practical applications.
As we have shown in the last part of this book, possibilities
exist that allow synthesizing of diamondoids both by electric
discharge and by pulsed laser plasmas generated in supercritical
fluids. Moreover, in principle, diamondoids can also be produced by
plasmas generated in atmospheric-pressure plasma microreactors.
However, compared to the synthesis in supercritical fluids, the
quantities obtained by this approach are much lower.
To advance the field of diamondoids and extend their use
in various applications, it is necessary to further investigate
possibilities for their synthesis. We hope that the present text can
serve as an inspiration for both experienced and young researchers
to engage in research on this fascinating class of nanomaterials so
that the field of diamondoids and also their applications can grow.
 Appendix

A.1 Character Code Tables of Diamondoids

For the sake of completeness, we list the character tables of the
different point groups of the most common diamondoids.

Table A.1 Character code table

for the C 1 point group

C1 E h=1
A 1

Table A.2 Character code table for the C s point group

Cs E σh h=2
A’ 1 1 x, y, R z x 2 , y 2 , z2 , x y
A” 1 −1 z, R x , R y yz, zx

Table A.3 Character code table for the C 2 point group

C2 E C2 h=2
A 1 1 z, R z x 2 , y 2 , z2 , x y
B 1 −1 x, y, R x , R y yz, zx

Table A.4 Character code table for the C 2ν point group

C 2ν E C2 σν (x z) σν (yz) h=4
A1 1 1 1 1 z x 2 , y 2 , z2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y zx
B2 1 −1 −1 1 y, R x yz
194 Appendix

Table A.5 Character code table for the C 2h point group

C 2h E C 2 (z) i σh h=4
Ag 1 1 1 1 Rz x 2 , y 2 , z2 , x y
Bg 1 −1 1 −1 Rx , R y x z, yz
Au 1 1 −1 −1 z
Bu 1 −1 −1 1 x, y

Table A.6 Character code table for the D3d point group

D3d E 2C 3 3C 2 i 2S6 3σd h = 12

A1g 1 1 1 1 1 1 x 2 + y 2 , z2
A2g 1 1 −1 1 1 −1 Rz
Eg 2 −1 0 2 −1 0 (R x , R y ) (x 2 − y 2 , x y) (zx, yz)
A1u 1 1 1 −1 −1 −1
A2u 1 1 −1 −1 −1 1 z
Eu 2 −1 0 −2 1 0 (x, y)

Table A.7 Character code table for the Td point group

D3d E 8C 3 3C 2 6S4 6σd h = 24

A1 1 1 1 1 1 x 2 + y 2 + z2
A2 1 1 1 −1 −1
E 2 −1 2 0 0 (2z2 − x 2 − y 2 , x 2 − y 2 )
T1 3 0 −1 1 −1 (R x , R y , R z )
T2 3 0 −1 −1 1 (x, y, z) (x y, yz, zx)
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 Index

1-MA, 185–88 dissociation of, 184

1-methyladamantane, 130, 185, face-fused, 14
187 functionalized, 95
2-MA, 185–89 lower solubility of, 173–74
2-methyladamantane, 44–45, precursor, 165, 179–81, 185,
152–54, 185, 187–88 187–89
1,4-dimethyladamantane, 186–88 solid, 60
1,4-DMA, 186–88 solubility of, 50, 53–54, 168
structure of, 12, 45, 120–21, 126
synthesis of, 121–22
ab initio calculations, 42, 156, 188 adamantane amine, 87
ab initio simulations, 71, 74, 149 adamantane cages, 17, 23, 25, 154,
ablated material, 159 184
ablation mechanisms, 157
adamantane centers, 25
absorption, 100, 159
adamantane concentration, 163
absorption measurements, 117
adamantane content, 181
abstraction, 189
adamantane derivatives, 87,
AC, see alternating current
90–96, 105, 186, 188
acceptor, 83
adamantane dimer, 14–15
electron pair, 83
adamantane framework, 151, 154
accumulation, 57, 112
adamantane reservoir, 143
acetone, 52, 124
acetylcholine, 89 adamantane units, 13–18, 23–25,
acquired spectra, 68, 71 30
activity, 86, 88, 91–92 adamantanone, 76–77
anti-Parkinsonian, 88 adamantine, 90
activity coefficients, 51–52 additives, 94, 96
AC voltage, 138, 143 hydrocarbon, 156
adamantane, 11–24, 31–33, 35–37, adsorption, 93–94
42–43, 45–46, 53–55, 59–62, aliphatic cage structures, 7
67–71, 76–79, 85–88, 90–93, alkanes, 14, 36, 82, 84, 103
119–22, 142–44, 151–56, alkyls, 187, 190
185–90 allotropes, 10
alkylated, 110 alternating current (AC), 137, 180
222 Index

alternative approaches, 101, artificial synthesis, 111, 120

123–24, 127, 141, 177, atmospheric pressure, 8, 133,
189 177–78, 189–90
Alzheimer patients, 89–90 atmospheric-pressure DBDs, 139
Alzheimer’s, 105 atomic hydrogen lines, 184
Alzheimer’s disease, 86, 89–90 atomic number, 10
amantadine, 87–90 atoms, 5, 11–12, 14–17, 19–21, 26,
amino acids, 112 31–34, 38, 41, 47, 49, 57,
angles, 11, 23, 97 63–64, 67, 69–70
bonding, 41 apical, 13
solid, 149 bridge, 20
angular displacements, 103 inclusion, 67
anomalies, critical, 136 attachment, 87, 90, 92–93
anthracene, 53, 55 average power consumption, 182
anticholinergic effects, 89 azidothymidine (AZT), 93
anti-Parkinson’s agents, 86 AZT, see azidothymidine
anti-Parkinson’s effects, 89
antitetramantane, 43, 119–20,
128–29 bacteria, 85, 111, 115
applications, 19, 33, 56, 81, 93, bandgap, 41, 57–63, 99
129, 134, 137, 159, 162, 174, direct, 60, 99
177, 190 experimental, 58
biotechnology, 56 bandgap tuning, 64, 99
common, 82 bands, 183–84
communication, 102 conduction, 98
medical, 93, 103–4 valence, 97
microelectronics, 99 band structure, 57–58, 60
pharmaceutical, 86–87, 90, 92 batch reactors, large-scale, 141
potential, 55 batch-type reactors, conventional,
spintronic, 106 189
applied mathematics, 23 binding, covalent, 93
approaches, 4, 8, 57, 61, 99, 103, binding energy, 64–66, 116
119–26, 128–30, 133, 141, binding strength, 94
156, 175, 190–92 bioapplications, 56
common, 127 biocompatibility, 7, 55–56, 93
continuous-flow, 144 biological applications, 49
effective, 156 biomarkers, 111
experimental, 133 biosensors, potential, 101
aqueous environment, 93 biosynthetic origin, 85
aqueous solutions, 53, 55 biotechnology, 6, 55–56, 81–82,
aromatic compounds, 116 86–87, 89, 91, 93–94, 101,
aromatic fractions, 85 105, 191
aromatic rings, 87 blood–brain barrier, 88
aromatics, 165, 172 blood cleansing, 94
 Index 223

bond lengths, 41 carbon, 7, 9–13, 19, 46, 56, 59, 84,

bonds, 11–12, 42–43, 60, 86, 97, 112, 189–90
174, 188 amorphous, 10
chemical, 10 sp2 -hybridized, 165
dangling, 152, 155 sp3 -hybridized, 165
double, 12 carbon allotropes, 10
hybridized, 12 carbon atoms, 19, 47, 53, 57, 100,
ionic, 86 147, 152–54
bond substitutions, 99 additional, 154
bottom electrodes, 179 single, 152
grounded, 179 carbon bonds, 149
brain tissue, 93 carbon cages, 12, 38
branched catamantanes, 32 carbon cage structure, 12
bridgeheads, 19–22 carbon chains, 19
bridges, 19–21 linear, 10
Brillouin zone, 58 carbon compounds, 84
building blocks, 5, 11, 103–4 carbon cycle, 111–12
ideal, 101 carbon fragments, 151
molecular, 4, 7, 101, 105 carbon framework, 7, 12–13, 57
subnanosized molecular, 95 carbon ions, 156
bulk diamond, 43, 45, 57–58, 60, carbon materials, 11, 70, 84
99 carbon nanomaterials, 7, 9, 11–12,
56, 68
carbon nanostructures, 11
cage arrangements, 24, 32 sp3 -hybridized, 11
cage closure reaction, 156 carbon nanotube (CNT), 7, 10–12,
cage network, 152 68, 70, 140
cage number, 17, 30, 133, 147, multiwall, 56
168 single-wall, 56
increasing, 24, 38, 71, 119, carbon sites, 152
163–64 carbon source, 40, 155, 184
cages, 17–18, 24–25, 30, 32, 34, 57, carbon structures, recognizable,
65–67, 120, 129, 147–48, 151, 111
167–68, 170, 172–74 carbon surface reactions, 110
cage structure, 86, 149 carbon vacancies, 101
calcium ions, 90 catagenesis, 85
calibration curve, 145, 167–68 catalysis, 128
cancer treatment, 94 catalysts, 121, 123–24, 126–29,
capacitance, 182 140
parasitic, 182 catamantanes
carbocation, 120 irregular, 30–31
carbocation equilibration linear, 32
reactions, 120 regular, 31, 34
carbohydrates, 112 cavitation bubble, 158–59, 162
224 Index

cell autofluorescence, 101 CO2 exchange, 112

cells, 6, 56, 85, 92, 101, 104, 142, CO2 gas, 162
146, 161, 180 coal, 110
cubic, 45 organic, 113
inner, 160–62 codes, 25, 30, 37
living, 101 dual graph, 169
low-temperature, 45 dualist, 23–25, 30
outer, 160–61 cognitive capabilities, reduced, 89
photovoltaic, 6 collection trap, 163, 180
primitive, 58 commercial adamantane, 163–64,
stainless steel, 161 166
cellular mechanisms, 101 complexity, 69, 119, 121, 130
cellular membranes, 90 components
centers, 13, 18, 23, 25, 100 electronic, 3, 5
color, 6 functional, 3–4
nitrogen vacancy, 100 compositions, 39, 184
chains, 19, 23 chemical, 115
side, 87, 90 ionic, 94
charge transfer mechanism, 98 compounds, 112
CH bands, 184, 188 adamantoid, 44
chemical formula, 26, 30–31, new, 42
33–34 polycyclic, 18
chemical potentials, 46 sugar, 112
chemical properties, 41–43, 45, 47, compressibility, 136
49, 51, 53, 55, 174 compression loop, 160
chemical shifts, 79 computer algorithms, 21
chemical vapor deposition (CVD), concentration, 38, 53, 82, 110–11,
40, 151, 178, 184, 141, 165–67, 180–81
chemical waste, 141 equilibrium drug, 88
chromatograms, 154, 180 estimated adamantane, 189
classification, 9, 11, 13–19, 21, 23, higher H2 , 184
25–27, 29, 31, 33 increased, 83
graph-based, 31 intracellular, 88
systematic, 18 known, 145
clustering, 99 lower, 189
molecular, 136 condensates, solid, 110
cluster ions, 134 condensation, 162
cluster radicals, 134 condensation loop, 143
clusters, 5, 39 conditions, 30, 53, 82, 85, 90, 111,
high-density, 189 134, 137, 140–42, 144, 157,
CNT, see carbon nanotube 161–62, 185, 189
CO2 , 46, 50–51, 53, 112, 135–36, ambient, 45, 102
159, 161, 170, 173–74, 178 atmospheric, 189
high-density, 162 harsh, 140
 Index 225

high-pressure, 50 cyclodecane, 14–15

preparation, 47 cyclodextrins, 86
pressure-temperature, 50 cycloheptatriene, 123, 125
conduction band minimum, 98 cyclohexamantane, 43, 70–71
connectivity, 23, 31 cyclohexane, 14–15, 30, 40, 52, 62,
cooling/heating circuit, 143, 160 135, 147, 162–70, 173–74,
cooling loop, 143 180
coordination, 33 cyclohexane concentration, 163
coronamantanes, 26 cyclohexane planes, 147
correlation, 46 cyclohexane solutions, 144, 167–68
cosolvent, 163, 165, 169, 174 cyclohexane trap, 180, 185
covalent bonding, 93 cyclooctatetraene dimer, 126–27
CP, see critical point cyclopentadiene, 122–24
cracking, 82–83, 85, 110–11
cracking experiment, 114
cracking process, 85 DBD, see dielectric barrier
critical point (CP), 134–36, 182 discharge
crude oil, 84, 109–10, 120–21, 146, DBD
148–50, 164, 181 large-area, 139
cryptophanes, 86 needle-type, 140
crystal, 37, 117 DBD electrodes, 137–38
crystal lattice, 43, 74 micromachined, 139
crystalline adamantane, 58–59, 99 DBD microfluidic reactors, 190
band structure of, 58 DBD plasmas, 139–40
crystalline diamondoids, 60, 100 decamantane, 26, 35, 39, 42,
crystalline form, 77 150–51, 156, 169, 171
crystallization, 117 compact, 171
crystal structures, 9, 34–37, 43–44, decomposition, 40, 155, 173
161 deformation, 164
crystal structures of adamantane, degeneration, reduced, 89
36–37 density, 53, 57–58, 63, 71, 76,
crystal structures of diamondoids, 98–99, 135–36, 161
9, 35 critical, 135
cubic diamond lattice, 13 critical molar, 135
cucurbiturils, 86 electron, 139
current limiter, 137 high, 134
curved structures, 12 high neutral, 139
CVD, see chemical vapor deposition density functional theory (DFT),
CVD process, 40 57, 63, 71, 76, 99
cycles, 19–20, 25–26, 139, 154 deposition, 5, 112, 157
closed, 19–20, 22 depths, 82, 110, 112–13, 179
largest closed, 21 channel, 183
longest, 21 photon absorption, 158
longest closed, 20 thermal diffusion, 158
226 Index

derivates, 181 diamond defect, 103

thiol, 66 diamond films, 184
derivatives, 79, 81–82, 84, 86, 88, diamond growth, 178
90, 92, 94, 96, 98, 100, 102, diamond hydrocarbons, 14, 38
104, 106, 154–55 diamondiods, 8, 21, 30, 33, 35, 42,
methyl, 152, 154 70, 76, 85, 96, 106, 129, 158,
possible, 154 169–70, 191
trimethyl, 155 diamond lattice, 12–16, 18, 23, 120
destruction, 85 diamond mechanosynthesis, 103
rapid, 85 diamond molecules, 7, 38, 171
detonation synthesis, 40, 45, 93 diamond nanocrystals, 38
DFT, see density functional theory diamondoid-based
DFT calculations, 99 mechanosynthesis toolset,
DFT simulations, 59 103
diamantane, 17–22, 24–25, 43–46, diamondoid baseline, 111
50–53, 62–64, 68–69, 77–79, diamondoid cages, 17, 36, 61, 67,
113–14, 121–26, 144–45, 146, 170
147–52, 154–56, 166–69, diamondoid clusters, 63
173–74, 185–87 diamondoid concentration, 82, 111
1-hydroxyl, 51 diamondoid content, 113
dissolved, 168 diamondoid derivatives, 56, 94
functionalized, 63–64, 74 diamondoid enantiomers, 115
refined, 117 diamondoid family, 31
retention time of, 169–70 diamondoid framework, 33
solubility of, 53 diamondoid groups, 31–32,
standard, 166 146–47
diamantane concentration, 167–68 diamondoid homologues, 44
diamantane growth, 189 diamondoid hydrocarbons, 7,
diamantane sources, 85 12–14, 16–17
diamantane structure, 122 diamondoid LUMO, 98
diamantane synthesis, 123, 125 diamondoid members, 19
diamond, 6, 9, 11–13, 45, 47, diamondoid molecules, 70, 98
57–58, 61, 68, 70, 96, 99–103, diamondoid monolayer structure,
105, 179, 182, 184 96
bucky, 39 diamondoid precursors, 114, 156
cubic, 10, 13 diamondoid reactions, 110, 121
hexagonal, 10 diamondoids
macroscopic, 12, 100 alkylated, 147
nanocrystalline, 184 branched, 23
ultrananocrystalline, 79, 184 chemically modified, 101
diamond cages, 37, 64 common, 193
diamond clusters, 39, 45, 47, 49 complex, 21
diamond core, 39, 158 dissociation of, 149–50
diamond crystal lattice, 101 eluted, 168
 Index 227

fingerprinting, 77 discharge plasmas, electric, 129,

higher-order, 102, 174–75 135
large, 100 diseases, 87, 89–92, 104
nanoscale, 96 brain-related, 89
nitrogen-functionalized, 95 common, 89
nomenclature of, 7, 9 neurodegenerative, 86
octahedral, 62 dispersion, 38, 94
saturated, 50 dissociate, 149, 154, 174
smallest, 13, 79, 191 dissociation, 149, 165, 188
solid, 7 preferential, 174
solubility of, 42, 50, 53 dissociation energy, 149, 156
stable, 149–50 dissolution, 112
sulfur-doped, 63 dopamine release, 90
symmetric, 35 doped diamondoids, 67
diamondoid SAMs, 96–98 doping, 6
diamondoid separation process, external, 99
115 internal, 99
push-pull, 99
diamondoid size, 59–60, 63, 99,
102 doping strategies, 99
drug carriers, 56
diamondoid structure, 12–13, 22,
47, 57 drug delivery, 56, 92–93, 101
drug delivery systems, 93–94
complex, 21
drug molecules, 94
stable, 150
drugs, 87, 90–94, 106
diamondoid synthesis, 184, 190
active antiviral, 90
diamondoid thiols, 65–66
adamantane-based, 90
diamondoid units, 93, 121
adsorption of, 93–94
diamond particles, 38
pharmaceutical, 89–90
diamond sensors, 103
drugs lipophilicity, 90
diamond surface, 103
DTA, see differential thermal
diamond synthesis, 185 analysis
diamond unit cell, 13, 100 dual graphs, 23
dielectric barrier discharge (DBD), dualist degree partition, 34
137, 159, 174, 178, 189 dualist graph codes, 23, 26
dielectric barriers, 138–39, 141 dualist graphs, 17–19, 22–26,
dielectric constant, 98, 135 30–32
diethyl ether, 122
differential thermal analysis (DTA),
43 edges, 10–11, 14, 16–17, 23
diffusivity, high, 134 cage structure, 64
dimensionality, 11 shared, 17
dimers, 152 electric discharges, 133, 136–37,
dimethyladamantane, 114, 154–55 140–43, 145, 147, 149,
direction vectors, 23–24 151–53, 155, 177, 180, 192
228 Index

electrode configuration, 138 energy minima, 103, 120, 129

electrode geometry, 139, 141, 143, enthalpies, 44, 51
190 gas-phase, 187
needle, 139 standard, 44, 130
point-to-point, 139 environmental fingerprinting, 82
electrodes, 137–39, 141–43, 179 environmental forensics, 82
arrayed mesh-type, 138 environments, supercritical, 140
high-voltage, 139, 141 etching, 5, 49
inner, 142 electrochemical, 138
large-area-gap, 139 ethane, 50, 53, 135
micromachined, 139 ethanol, 95, 135
needle, 139–40 ethyl acetate, 52, 135
needle-type, 137 ethyladamantanes, 114
pointed, 137 evaporation, 156
electron densities, high, 139 evolution, 3–4
electron emission, 95, 97–98 evolution curve, 85
electronic circuits, 3 experimental conditions, 140, 142,
electronic structure, 10, 41–42, 57, 146, 162, 166, 180–84
96, 191 experimental data, 53, 57
electron ionization, 154 experimental equipment, 137
electron microscopy, 98, 110 experimental measurements, 68
electrons, 83, 97–99, 134, 158 experimental Raman spectra,
unpaired, 152 70–74
elements, abundant, 7 experimental setup, 141–43, 160,
elute, 170–71 179
elution times, 170 experimental spectra, 74
emission, 97, 100, 103, 184 experiments, 82, 96, 102, 114,
narrow, 101 149–51, 160–61
optical, 185 ablation, 163
soft X-ray, 59 batch, 145
emission spectra, optical, 183–84 batch-type, 148, 150
emitters, bright, 101 continuous-flow, 146
enantiomerism, 26 flow, 150
enantiomers, 68, 116 preliminary, 101
energy, 46–47, 58, 149 exploration, 50
bonding, 188 gas reservoir, 81
ground-state, 188 explosives, 110
high dissociation, 150 exposure, higher, 93
ionization, 77 exposure time, 113
kinetic, 97–98
lower, 59
orbital, 63, 66 fabrication, 3, 39, 128–29, 157,
total, 46 161, 192
vibrational, 46 synthetic, 122
 Index 229

face-centered-cubic (fcc), 36–37 saturated oil, 85

face-fused structures, 17 solid mole, 51
faces, 13–14, 16, 19, 23 fragmentation patterns, 185
shared, 16 fragments
fatty acids, 88 carbon-containing, 190
fcc, see face-centered-cubic hydrocarbon, 149
features frequency, 90, 138, 142, 180
main, 57, 77, 167
applied, 144, 181
spectral, 35, 68–69
ultrahigh, 190
vibrational, 68, 71
fullerene C60, 68, 70
feature sizes, 4–5
Fermi level, 98 fullerene network, 152
fields, 6, 8, 82, 100, 128, 159, fullerenes, 7, 10–12, 39, 152
191–92 functional groups, 38–39, 53, 57,
dipole, 103 64, 90, 93, 99
electric, 137 functionality, 4
fin-shaped, 3 functionalization, 7, 33, 39, 41, 57,
plasma reaction, 136 61, 64, 74, 119, 126, 158
technological, 7, 191 functionalization strategies, 63
films, 99 functionalized diamondoids, 21,
diamondoid/bromide, 99 76, 96
nanocrystalline, 38 function of pressure, 43–44
self-adhesive UV photosensitive, function of solvent density, 50–51
179 function of time, 3, 113
thin, 141 furnace, 117
finFET, see fin-shaped field-effect two-zone, 116–17
transistor
fused silica capillaries, 141, 143
fin-shaped field-effect transistor
(finFET), 4–5
flow rates, 141–43, 146, 149–51,
gap distance, 137, 139, 142
178
gas chromatography, 77, 142,
fixed, 181
166–67, 169, 171, 180
highest, 151
gas chromatography–mass
fluid, 50, 94, 134–35, 142, 158–59,
spectrometry (GC-MS), 166,
161–62
181
fluidic channels, 141, 179
fluid temperature, 142 gas compositions, 180, 183–86,
fluorescent molecule, 6 190
fluorescent nanodiamonds, single, gas condensates, 83, 115
101 natural, 82
formation energies, 47–48 gas constant, universal, 52
formation mechanisms, 85 gaseous environments, 157
fractions, 38, 52 gaseous states, 136
high-molecular-mass, 83 gaseous systems, 53
230 Index

gases, 53, 82–84, 109, 111, 113, GC-MS spectra of diamondoids,

115, 117, 134, 136, 159–61, 147
163, 178, 180, 187, 189 GC-MS spectrum of diamantane,
compressed, 161 147
natural, 50, 84, 106, 111, 191 GC oven temperature, 170, 172
normal, 110 GC retention time, 144, 148, 152
perfect, 181 Ge nanoparticles, 97
plasma, 187 genetic material, 88
pressurized, 161 geological times, long, 113
reactant, 180 glass, 113, 179
solubility of diamondoids in, 50 glass microreactors, 179
source, 179 glass slides, 182
gas exploration, 53, 110, 115 glutamate, 89–90
gas fields, 82 gold, 6, 98
gas formation, 113 gold nanoparticles, 161
gas gap, 182 graphene, 7, 10–12
graphene precursor, 11
gas mixtures, 180–81, 185, 187
graphite, 6, 10–11, 45, 68, 70
gas phase, 38
highly oriented pyrolitic, 162
gas reservoirs, 8, 50, 77, 83, 85,
groups, 12, 15–17, 32, 34, 43, 45,
110–11, 128, 133
81, 95, 128, 146–47, 149–51,
gas temperature, 137
161, 170–71
gastrointestinal cramps, 89
corresponding space, 37
gate widths, 5 electron-withdrawing, 99
reducing, 5 first, 147, 150
GC column, 172 higher, 32
GC-MS, see gas last, 17
chromatography–mass main, 15–16, 26
spectrometry new, 31
GC-MS analyses, 149–50, 168, oxygen-containing, 38
171–72 point, 30, 193–94
GC-MS analysis, 151, 185 polar, 50
GC-MS mass spectra, 167 propyl, 154
GC-MS measurements, 142, 146, secondary, 34
154, 168, 170–71, 174, 185, single thiol, 65
188, 190 space, 37, 45
GC-MS retention times, 169, 172 symmetry, 35
GC-MS scan mode, 152 trimethylenemethane, 30
GC-MS scan rate, 168 growth, 40, 116, 150, 152, 159,
GC-MS signals, 169 178, 184
GC-MS SIM, 147 closed network, 152
GC-MS SIM peak area, 168 continuous gas-phase, 178
GC-MS spectra, 156 conventional CVD, 184
GC-MS spectra analysis, 154 diamond film, 86, 151
 Index 231

diamondoid, 156 high-performance liquid

nanocrystal, 157 chromatography (HPLC),
nucleation, 159 115–17
selective, 156 high-pressure cell, 143, 159–62
growth mechanism, 40, 155 high-pressure equipment,
guest molecules, 86 specialized, 177–78
high-pressure pump, 161
high-temperature polymers, 95
HABst tool, 103, 105 high-voltage amplifier, 180
histidine residue, 88
Hβ emission, 184
HIV, see human immunodeficiency
H/C ratio, 174
virus
heat, 124, 126–27, 136
HOMO, see highest occupied
desorption, 94 molecular orbital
heat capacity, 135 homoadamantane, 153–54
heat exchange, rapid, 141 HOMO-LUMO gap, 59, 64–65
heating, rapid, 160 relative, 67
heating circuit, 143 HOPG, see highly oriented pyrolytic
heating element, 117 graphite
heat resistance HOPG targets, 163
high, 82 host–guest chemistry, 6, 86–87
increased, 95 HPLC
heptacyclooctadecanes, 127–28 reverse-phase, 116
heptamantane, 24–25, 30, 73, selective, 115–16
148–51, 169 shape-selective, 116
heptane, 52, 135 HPLC, see high-performance liquid
chromatography
herpes zoster neuralgia, 87
human immunodeficiency virus
heteroatoms, 61
(HIV), 86, 92
hexamantane, 26, 30, 61, 68,
hybridizations, 7, 9–12, 70
148–51, 163–64, 169–71
hybrids, 10
hexogen molecules, 40 hydrocarbon radicals, 151
H-functionalized diamondoids, 41 hydrocarbons, 13–15, 85, 110,
higher diamondoids, 17–18, 35, 165
77–78, 106, 109, 111, 116, diamond-structured, 165
119–20, 128, 142, 147, 149, multiringed terpene, 83
152, 156, 191–92 nondiamondoid, 14–15, 166,
synthesis of, 120, 126 173
unsubstituted, 171 polycyclic, 83–84
highest occupied molecular orbital polycyclic aromatic, 53
(HOMO), 42, 59–60, 66 hydrogen, 38, 47–48, 152, 178,
high-frequency torch, 139 180–81, 188
highly oriented pyrolytic graphite abstracting, 103
(HOPG), 158, 162 atomic, 184
232 Index

hydrogen abstraction, 105, 187 intensity ratio, 144

repeated, 189–90 interlayer distance, 115
hydrogenation, 123 intermediate structures, 152, 154
hydrogen atoms, 12–13, 18, 39, 46, intermolecular level, 57
67, 103, 147, 149, 152, intermolecular packing, 43
154–55 intersection, 62
axial, 30 interstellar dust, 38
hydrogen bonds, 86, 88 ionization degree, 139–40
dangling, 156 ionization potential (IP), 64–65
hydrogen content, 45 ionized cluster, 134
hydrogen coverage, 47 ionized molecule, double, 77
hydrogen removal, 152 IP, see ionization potential
hydrogen terminations, 7, 14, 42, IP trend, 65
47, 64, 105, 145, 156 irradiation, 158, 161
complete, 39, 49 isolation, 43, 106–7, 109–10, 112,
hydrophobic interactions, 86 114, 116, 150
hysteresis, large, 43 isomers, 30–31, 50, 120, 123, 127,
170–71
ITO, see indium tin oxide
imaging, 101, 103 ITO film, 143
real-time, 101 IUPAC names, 21
impairment scores, 89 official, 19, 32
implementation, 101
impurities, 117
inactive mode, 74 Katz dimer, 123–24
incontinence, 89 kerogen component, 113
indicators, 111 kerogens, 84–85, 111–12, 114
indices, lowest, 24 organic, 85
indirect-bandgap materials, 100 kinetics, 94
indium tin oxide (ITO), 141,
179
industrial applications, 5 laboratories, scientific, 5
inertness, 55–56 laser, 160, 162–63
infections, 91 pulsed, 160
influenza, 87–88, 90 laser ablation, pulsed, 157, 159–60
influenza virus, 86–88 laser pulse, 157–59, 161
infrared spectra, 68, 71, 76 femtosecond, 157
intensities, 61, 145, 153, 165–66, laser spot, 160
184, 187 leakage currents, 5
area, 145 Lewis acid, 83, 122
fluorescence, 103 Lewis acid catalyst, 83
high, 160 Lewis base, 83
reduced, 117 light, pulsed laser, 160
intensity peak, highest, 154 lightheadedness, 88
 Index 233

light sources, 4–5, 69 LUMO, see lowest unoccupied

polarized, 68 molecular orbital
pulsed, 98
Li ion batteries, 6
limitations, 4–5, 129 macrodiamonds, 102, 110
linear chain, 12 macromolecules, 93, 112
linear combination, 10 macroreactors, 178
linear fit, 62 macroscale diamonds, 8, 57
linear molecules, 70 macroscale reactors, 141
linear regression, 145 macroscale reactor systems, 178
linear structures, 12 macroscopic masks, 4
lipidic membranes, 92 magnetic fields, 102–3
magnetic properties, 9
lipids, 88, 90, 93
magnetic resonance force
lipophilicity, 92
microscopy (MRFM), 102
liquefaction loop, 160–62
magnetic signals, 102
liquid-based chemistry synthesis,
magnetism-based data storage, 102
189
mass spectra, 57, 77–78, 144–45,
liquid CO2 , 162
147, 153–55, 166–67, 171–72,
liquid nitrogen, 161–62
180, 185–86
liquid phase, 134 experimental, 181
liquids, 45–46, 83, 134, 136, reference, 181
158–59, 161 mass spectrometer, 154, 156
confining, 157 mass spectrometry, 77, 142,
liquid states, 136 166–67, 169, 171, 180
liquid trap, 161 mass spectrum, 144–45, 147–48,
liquid water, 158 152–54, 167, 174, 185–86
lithography, 4, 179 reference, 153
electron beam, 98 material ejection, 157–58
local energy maxima, 149 materials processing, 134, 157
local minima, 111 materials synthesis, 141
long-term annealing, 49 material transistors, 6
lower diamondoids, 17–18, 24–26, maturation levels, higher, 85
35–36, 43, 60, 68–69, 71, maturity, 82–83
77–78, 83–85, 111, 119–20, maximal exposure, 94
128, 147, 149, 152 maximum
lower diamondoid synthesis, 120, local, 147
128 valence band, 58
lower-energy levels, 98 maximum energy, 163
lowest unoccupied molecular maximum fluence, 163
orbital (LUMO), 42, 59–60, 66, mechanosynthesis, 105
97–98 diamondoid-based, 104
low-frequency domains, 71 media, 134, 159
low-temperature phase, 45 high-pressure, 136
234 Index

medicine, 7, 55–56, 81, 86–87, 89, high-pressure, 178

91, 93–94, 105, 191 microcapillary, 145
medium, 168, 174 microplasmas, 131, 133, 156, 178
high-pressure, 157 high-pressure microfluidic, 178
melanoid reaction, 112 microreactors, 141, 156, 180–81
melting points, 36 continuous-flow, 178
memantine, 87–88, 90 custom-made chip, 179
metabolism, 56 quartz, 179
metallic coatings, 96 microreactor systems, 141–43, 178
metallic nanoparticles, 6–7, 56, microscale reactors, 141, 189
158, 178 microscopic fluid structure, 136
metal nanoparticles, noble, 161 minerals, clay, 113
metals, heavy, 94 models, 52, 89, 113
meteorites, 38, 45, 110 ball-and-stick, 42
methane, 14, 47, 50, 84, 178,
modes, 70
180–81
active vibration, 164
methanol, 95, 135
symmetric, 69
methods
mode spectra, 147
advanced refinement, 116
modifications, 61, 74
conventional organic chemical,
molecular diamonds, 12
174
conventional organic chemical molecular formula, 33–34, 169
synthesis, 111 molecular fossils, 111
conventional top-down molecular ion, 77–78, 144, 147,
fabrication, 5 186
spectroscopic, 57 charged, 171
vibrational spectroscopy, 77, 79 molecular ion base peaks, strong,
methyladamantanes, 114, 152, 187 147
methyl attachment, 152, 189 molecular ion peak, 145, 153–54,
methyldiamantanes, 111, 114 167, 170, 172, 185
methyl groups, 152, 154, 156, 189 large, 172
methyl radicals, 152, 155–56 prominent, 77
micoreactor channel, 179 respective, 154
microcapillary reactors, 142, 144 strong, 171
microchannels, 179, 182 molecular level, 103
microchip reactors, 179 molecular machines, 101, 103
microelectronic devices, 157 molecular masses, 13, 30–31, 36,
microfluidic reactor, 178–79, 182 148, 180
high-pressure, 178, 180 relative, 144, 146–48, 152, 154,
microfluidic reactor systems, 141 185
microplasma reactors, 177, 179, molecular mechanics, 43, 89
182 molecular processes, 6
atmospheric-pressure, 178 molecular robots, 104
continuous-flow, 178 molecular rotors, 103
 Index 235

molecular structures, 13–14, nanocrystals, 103

16–18, 21, 32, 35–36, 41, 64, silicon, 161
67, 87, 90, 92–93, 95–97, nanodiamond, 158
103–4, 151, 153 nanodiamond formation, 110
regular, 36 nanodiamondoids, 45, 56
well-defined, 94 nanodiamond particles, 94, 158
molecular symmetries, 7 commercial, 93
molecular symmetry, 34–35, 37 nanodiamond purity, 94
molecular weight (MW), 31–32, 82, nanodiamonds, 7–12, 38–40,
142, 146, 166, 169–74 47–49, 55–57, 85, 93–94,
molecules, 13–15, 17, 19–20, 100–102, 105, 158, 177–78
25–26, 34–35, 39, 43, 45, 59, applications of, 94
63, 134, 147, 150, 170, 174 detonation, 38
absorbed, 115 doped, 38
base, 147 faceted, 49
closed-shell, 77 nanodiamond structure, stable, 48
guest, 86 nanodiamond synthesis, 39, 158
host, 86 nanoelectronics, 7, 191
hydrocarbon, 172 nanomarkers, 6
ionized, 77 nanomaterials, 5, 7, 81, 129, 156,
isolated, 60, 74 159, 192
large, 85, 112 nanomedicine, 104
organic, 103 nanometers, 3, 5
monocarbon radicals, 40 nanoparticles, 4, 6, 55, 158, 161
monochromatic electron fluorescent, 6
photoemission, 96 semiconductor, 6
monocrystal, 94 nanorobots, 101, 103–4
monolayers, 93, 103 nanoscale, 10–11
self-assembled, 96–98 nanosecond lasers, 157
montmorillonite, 113, 115 nanosecond pulses, 157
Moore’s law, 3–4 nanoseconds, 137
morphological behaviors, 96 nanostructures, self-assembled, 95
morphology, 99, 178 nanotechnology, 9, 81, 94–95, 97,
motor ability, 89 99, 103
motor capacities, 89 nanowires, 4–5
MRFM, see magnetic resonance semiconductor, 178
force microscopy tungsten oxide, 139
MW, see molecular weight naphthalene, 53
MW groups, 170–73 natural gas production, 50
natural sources, 84, 109–11, 113
NEA, see negative electron affinity
naming conventions, 18, 191 NEA of diamondoids, 97
naming scheme, 18 near-edge X-ray absorption fine
systematic IUPAC, 18 structure (NEXAFS), 97
236 Index

needles, 138 octamantanes, 148, 150–51, 169

needle-type DBD, 138 OES, see optical emission
negative electron affinity (NEA), spectroscopy
96, 98–99 OES measurements, 184–85
neurotransmitter, 89 oil, 8, 50, 77, 81–85, 110–11,
neutral radicals, 184, 189 113–15, 117, 121
NEXAFS, see near-edge X-ray natural, 85, 110–11, 128, 133
absorption fine structure uncracked, 111
nitric acid, 39 oil condensates, 115–16
nitrogen, 38, 100 oil deadline, 82, 110
nitrogen impurities, 101 oil destruction, 82
nitrogen vacancy (NV), 100 oil exploration, 50, 82–83, 85
nitrogen vacancy defects, 6 oil formation, 114
NMDA, see N-methlyl-D-aspartate oil generation, 113
NMDA antagonist, 90 oil reservoirs, 50, 53, 84, 106,
NMDA receptor, 89 109–12, 114, 116, 191
NMDA receptor modulator, 92 oil sources, 110
N-methlyl-D-aspartate (NMDA), 89 oil spills, 83
NMR, see nuclear magnetic optical emission spectroscopy
resonance (OES), 181, 183, 185, 188
nomenclature, 9–10, 12, 14, 16–18, optimization, 3–4
20, 22–24, 26, 28, 30, 32, 34, optoelectronics, 82
36, 38, 40 orbitals, 10–11, 59
nondiamondoids, 13–14, 116, 166, hybridized, 10
174 lowest unoccupied, 59
nonequilibrium, 137 lowest unoccupied molecular,
nonlinear molecules, 70 42, 97
nonplanar transistor designs, 3 sp3 -hybridized, 11
nontoxicity, 7 valence, 10
nonuniform size, 39 order, 3, 5, 35, 38, 77–78, 110–11,
norbornene, 122–24 120, 122–23, 137, 139, 142,
norbornene dimer, 122–23 147–49, 182, 189, 192
nuclear magnetic resonance organic chemistry, 50, 133, 192
(NMR), 79 organic chemistry synthesis,
nucleic acids, 93 conventional, 190
NV, see nitrogen vacancy organic compounds, soluble, 112
NV centers, 100–103, 106 organic material, 85, 103, 112
NV color centers, 102 organic matter, 85, 111–12
NV defect, 102 organic precursors, 83
organic solvents, 41–42, 50, 85,
112
observation, 45, 149 organic synthesis, 106, 120–21,
observed spectra, 154, 173 130
octadecane, 21–22 conventional, 122, 129
 Index 237

organic synthesis of diamondoids, base, 186

119–20, 122, 124, 126, current, 182
128–30, 133 discharge, 182
organisms, 6, 56, 93–94, 112 distinctive, 35
living, 85 dominant, 186
oil precursor, 111 fragment, 167, 172, 186
organs, 6, 56–57 large, 144
orientation, 97 largest, 154
orthorhombic, 36–37 observed, 172
oscilloscope, 143 prominent, 184–85
outlet, 143, 160–61, 179, 182 strong, 165–66
outlet zones, 182 well-resolved, 163
overloading, 94 pentacyclotetradecane, 125
overstimulation, 89–90 pentamantane, 18, 23, 26, 30–31,
oxidation, 93, 112 35–37, 61–62, 67–68, 72–74,
direct, 111 147–51
oxidizing acids, 112 perimantanes, 25–28, 32
oxidizing agents, 85 petroleum, 82, 85, 110, 113, 170
oxygen, 38, 49 petroleum reservoirs, 82
pharmaceutics, 7, 56, 81–82,
86–87, 89–91, 93, 191
PAH, see polycylcic aromatic phase change, 43, 45
hydrocarbon phase diagrams, 45, 134
paraffin, 165, 172 phases, 44–45, 134
parallel microchannels, 181 gaseous, 134, 136
Parkinson patients, 89–90 solid, 34–35, 45–46
Parkinson’s disease, 89–90, 106 phenanthrene, 53, 55
particle diameter, 47 perhydrogenated, 83–84
particles, 60, 99, 117 phonons, 98, 158
fluorescent, 6 photocathode device, 99
solid, 142 photocathodes, 98
particle sizes, 38, 48, 141 photochemical, 156
partition coefficient, higher, 88 photoelectron, 98
partitions, corresponding, 33 photoelectron emission, 98
patients, 89–90 monochromatic, 96
patterning, 5–6 spontaneous, 98
peak areas, 188 photoelectron emission spectra, 97
peak intensity, 72–73, 145 photoemission spectra, 96
integrated TIC, 186 photo-ion, 61–62
peaks, 34, 68, 71, 77–78, 142, 144, photo-ionization level, 62
147–48, 152, 154, 165–66, photons, 98, 100, 158
168, 171–73, 181, 185–86 photopolymers, 95
absorbance, 117 photoresists, 95–96
additional, 74 photosensitizing agents, 122
238 Index

physiological action, 89 positions, 19–21, 23, 31–32, 57, 64,

pillararenes, 86 66, 117, 156, 182
PLA, see pulsed laser ablation median, 66
PLA plasmas, 158 relative energy, 59
plasma activation, 156 powder blasting, 179
plasma chemistry, 5, 190 power consumption, 142, 182
plasma conditions, 184 power supply, 138
plasma CVD, 151 precipitation, 112
plasma emission, 184 precursor gases, 184
plasma formation mechanism, 158 precursors, 40, 120–29, 133,
plasma gas chemistry, 187 142–43, 156, 178, 189
plasma gas compositions, 188 main, 111–12
plasma generation, 136–37, 139, precursor size, 178
143, 182 predictions, 5, 185
plasma microreactors, 178, 189 premature release, 94
atmospheric-pressure, 192 presolar origin, 110
pressure, 43–44, 46, 53, 85,
high-pressure, 143
134–35, 141–44, 158, 160–61,
plasma plume, 157–59
163, 180–81, 184, 189
plasmas, 8, 134, 136–37, 139–40,
effect of, 43, 76
142, 156–57, 159–60, 162,
high, 43, 53, 137, 140–41, 159,
177, 179, 181–82, 188–90,
190
192
sublimation, 55
conventional gaseous, 134
pressure conditions, 50
gaseous, 134
pressure indicators, 180
low-temperature, 137, 139
pressure range, 54, 137
reactive, 139
pressure sensor, 161
plasma species, 190 pressure values, 142, 158
plastic phase, premelting, 69 probes, 81
platinum, 123, 128 fluorescent, 56
platinum dioxide, 122 high-voltage, 143
polar, 38, 53, 116 small magnetic, 102
polar compounds, 115–16 processes, 6, 98, 100, 111, 113, 155
polar fractions, 84 adsorption/desorption, 93
polarization tensor, 74 batch-type, 178
polar solvents, 51, 53 continuous-flow, 178
polycylcic aromatic hydrocarbon conventional microfabrication, 5
(PAH), 53 conventional SCF, 140
polymerization, 112 electron ionization, 154
polymers, 85, 95, 112 microbiological, 111
nanocomposite, 95 natural, 111
polysaccharides, 93 nonequilibrium, 158
polyynes, 11–12 plasma-based, 190
porous networks, 102 process flow diagram, 143
 Index 239

processing, 4–5 purity, 94, 144, 162, 166

biological, 112 high, 38
products, 77, 95, 142, 144–45, 150, pyrobitumen, 82–83, 111
153, 163–68, 174, 180, pyrolysis, 115–16, 163–64, 166,
185–87, 190 172–73
gaseous, 156 pyrolysis experiments, 172–73
intermediate, 123, 142, 151,
154, 156
natural, 111 quantities, 35, 77–78, 88–89, 129,
reaction, 174 139, 177, 186, 188, 190–92
side, 120 large, 44, 56, 77, 106, 123
proliferation, 22 lower, 185, 190
properties, 13, 45, 57, 81, 87–88, small, 77
94, 104, 135–36, 158 quantum communication, 8,
attractive, 92 100–102, 106
basic, 11 quantum computing, 8, 101–2, 106
electronic, 57 quantum optics, 102
main, 134, 137 quantum revolution, 100
molecular, 137 quartz tube, 117
physicochemical, 156 sealed, 117
special, 81
structural, 43
thermophysical, 136 racemic mixture, 69
transport, 136 radicals, basic, 40
vibrational, 191 radio frequency (RF), 137, 139
prophylaxis, 88 Raman and infrared spectra, 71
propyladamantanes, 154 Raman measurements, 35
proteins, 93–94, 112 Raman peaks, intense, 166
proton spins, 103 Raman scattering, 74, 165
pulsed laser ablation (PLA), 136, Raman shift, 70–74, 76, 164
152, 157–75, 178, 190 Raman signal, 165
pulsed laser ablation plasmas, 136, Raman spectra, 68–71, 74, 76–77,
178 142, 163–65, 174
pulsed laser ablation processes, characteristic, 71
190 measured, 165
pulsed laser plasmas, 129, 133, real, 74
157–62, 164, 166, 168, 170, Raman spectroscopy, 35, 68, 70
172, 177, 192 Raman spectrum, 163
pulse width, 163 Raman wavelengths, 71
purification, 39, 50, 109 range, 7, 38, 49, 81–82, 89, 91, 105,
chemical, 39 142, 157, 163, 165, 169,
purification process, 116 180–82, 184, 191
purification techniques, 117 low frequency, 74
purified material, 77 maturity, 85
240 Index

microwave, 190 region, 44, 71–73, 109, 111

wavenumber, 165 high-energy, 165–66
rates high-wavenumber, 166
fast heating, 171 low-energy, 165
optical, 103 near-infrared, 101
production, 166–67, 173–74 relationship, energy dispersion, 60
repetition, 140, 163 reproducibility, 141, 178
scan, 171 reservoirs, 106, 109, 111, 113, 191
ratio residence times, 141, 144, 151,
high H/C, 174 156, 181
mass-to-charge, 144 increasing, 151
signal-to-noise, 168 longest, 150–51
reaction intermediates, 111, 129, shortest, 151
155, 180–81, 185–87, 189 resin, 84–85, 95
reaction mechanisms, 126, 185, resistive heaters, 180
189 resolution, 5, 171
reaction pathways, 111, 129–30, lower scanning, 172
133, 156 nanometer, 103
reactions, 49, 83, 120–29, 149, retention, relative, 172
152, 174, 178, 189 retention times, 144–45, 147, 153,
batch-type, 149 166–67, 169, 171–72, 181,
chemical, 134, 141 185, 187
competing, 174 distinct, 170
dissociation, 150 GC-MS, 168
flow-type, 150 reference, 170
free-radical, 152 relative, 169–70
stepwise, 190 reuptake, diminished, 89
ultrafast, 141 RF, see radio frequency
reaction schemes, 121–25, 128, RF plasmas, 139
130 rimantadine, 87–89
reaction steps, 122, 126, 187 rings, 127, 153
reaction volumes, small, 141 closed, 19, 21
reactivity, 31, 33, 42 rocks, 85
reactor, 141, 143, 178–80, 182 sedimentary, 84–85, 112–13
reactor geometry, 181 silicate, 112
reactors, large-scale, 141 room temperature, 45, 101, 103,
rearrangements, 126–28 135, 159, 165
carbocation, 83 rotary pump, 180
catalyzed, 83–84 route, synthetic, 128
solid catalyst-mediated, 128
stabilomeric, 122
receptor/ion-channel complexes, safety, improved, 141
90 samples
receptors, 89–90 collected, 180
 Index 241

mouse, 57 SCF medium, 161

purified, 77 SCF microfluidic reactors, 156
reference, 186 SCF phases, 135–36
refined, 117 SCF plasma microreactor, 156
refined diamantane, 117 SCF plasmas, 134, 140, 148–50,
standard, 144–45, 147, 166–67, 155
185–86 SCF plasma synthesis, 140
synthesized, 185 SCF synthesis, 140
sample solution, 168 scissions, 19
SAMs, large-area, 96 S-doped diamondoids, 66
SAM, see self-assembled monolayer sediments, 85, 110, 112
scaffolds, 87, 90 SAM, see self-assembled
scale monolayer, 96–98
atomic, 102 supercritical fluid (SCF), 133–34,
color, 135 136–37, 139, 141, 159, 161,
industrial, 191 175, 177, 189–90
macroscopic, 10
nanometer, 103
scan mode, 180 TIC, see total ion chromatogram
scanning probe, 103 total ion chromatogram (TIC), 180,
scan times, 171 188
SCF, see supercritical fluid
properties of, 136
SCF conditions, 140, 161 von Baeyer designation, 21
SCF media, 159 von Baeyer names, 21