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functional applications
Cite this: J. Mater. Chem. C, 2015,
3, 6947
Yingjie Zhou,abc Alex D. Brittain,b Deyuan Kong,d Min Xiao,c Yuezhong Meng*c and
Luyi Sun*b

Diamondoids, a group of hydrocarbon cage molecules that resemble diamond lattice, are attracting
increasing interest in the past decade. Their diamond-like structure warrants that diamondoids inherit
the superior properties of diamond at nanoscale, including exceptional hardness and stiffness, high
thermal stability, high chemical resistance, unique optical properties and fluorescence, and excellent
biocompatibility. To effectively take advantage of the fascinating properties of diamondoids, they must be
properly functionalized so that they can be covalently incorporated into the host systems or compatibly
mixed with the hosts. Herein, the origin, synthesis, derivatization, and application of diamondoids are
Received 15th May 2015, reviewed. In particular, how the derivatized diamondoids for various functional applications, including
Accepted 9th June 2015 pharmaceuticals, polymers, fine chemicals, nanomaterials, and optical devices, are discussed. It is hoped
DOI: 10.1039/c5tc01377a that this review article can attract more interest in diamondoids, which in turn helps motivate the
development of new synthesis and application of diamondoids and their derivatives so that this group of
www.rsc.org/MaterialsC unique molecules can bring more benefits.

1. Introduction Therefore, diamondoids have been broadly adopted for various

applications in recent years.4–7
Nanostructured materials have attracted significant interest and The general chemical formula of diamondoid hydrocarbons
have also found widespread application in the past decade.1 is C4n+6H4n+12 (where n is the number of diamond cage subunit),
Nanostructured materials are often assembled from nanoscale or which are composed of all trans-fused cyclohexane rings in
even molecular scale building blocks with unique characteristics. ‘‘chair’’ conformation. The regular structural series of hydrogen-
Graphene, fullerene, carbon nanotubes, various nanoparticles/ terminated diamonds include lower diamondoids (o1 nm),
nanowires/nanosheets/nanocrystals, amino acids, DNAs, etc., higher diamondoids (B1–2 nm), nanocrystalline and chemical
are all well-known as functional building blocks.2 Diamondoids vapor deposition diamonds (B2 nm to microns), and macro-
are a group of hydrocarbon cage molecules that resemble scopic diamonds.8,9
diamond lattice. Because of such a unique molecular structure, As the smallest member of the diamondoid series, adamantane
diamondoids possess high thermal stability (melting point 269 1C, (C10H16) consists of a single cage-shaped diamond crystal subunit
the highest melting hydrocarbons known),3 superior chemical and dangling carbon bonds that are terminated with hydrogen.
resistance, wide optical transparency, marvelous lubricating perfor- The successive larger diamondoids are formed by connecting
mance, and outstanding mechanical and electrical properties.4–7 additional diamond crystal cages. Diamantane (C14H20) contains
two face-fused cages, triamantane (C18H24) has three, and so on
a
School of Physics and Optoelectronic Engineering, Nanjing University of (Fig. 1). Tetramantane (C22H28) is the first un-substituted
Information Science & Technology, 219 Ningliu Road, Nanjing, Jiangsu, diamondoid with chirality, and it has four different isomers
210044, China that result from alternate face-fusing of the four cages. The
b
Department of Chemical & Biomolecular Engineering and Polymer Program,
higher diamondoids show an abundant expansion of structural
Institute of Materials Science, University of Connecticut, Storrs,
Connecticut 06269, USA. E-mail: [email protected]; Fax: +1 (860) 486-4745;
complexity and varieties of molecular geometries.8 Consequently,
Tel: +1 (860) 486-6895 they can be considered as hydrogen-terminated diamonds with
c
The Key Laboratory of Low-carbon Chemistry & Energy Conservation of diverse isomeric and structural variants. A lot of reports about the
Guangdong Province/State Key Laboratory of Optoelectronic Materials and isolation, synthesis, derivatization, and application of diamond-
Technologies, Sun Yat-sen University, Guangzhou 510275, China.
oids have been published since their discovery, especially in the
E-mail: [email protected]; Fax: +86 20-8411-4113;
Tel: +86 20-8411-4113
past decade.
d
Integrated Laboratory Technologies, Chevron Energy Technology Company, Adamantane was initially discovered and isolated in petroleum in
Richmond, CA 94802, USA 1933.11 Higher diamondoids including triamantane, tetramantane,

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Scheme 1 Prelog’s method to synthesize adamantane.

Fig. 1 Structures of adamantane (left), diamantane (center), and triaman- isomerization of dicyclopentadiene (Scheme 2) using aluminum
tane (right) shown in the diamond lattice (reprinted with permission from
trichloride as a catalyst.24 The synthetic route was simple, and
the American Association for the Advancement of Science).10
the yield could be increased to up to 30–40%. Later on, the yield
was further improved to ca. 60% by modifying the catalysts and
pentamantane, and hexamantane were first discovered from optimizing the reaction conditions.5 This method is the current
petroleum in the early 1990s.12,13 However, due to the technical commercial process to produce adamantane. In the future, the
challenge they were not isolated from petroleum until 2003 by main goal in synthesizing adamantane is to further improve the
Dahl et al.8 Therefore, their chemical properties have been less yield and reduce the side reactions (byproducts).
studied and reported in the literatures. Lab synthesis of ada- Various attempts were made to prepare diamantane or higher
mantane, diamantane, and certain higher diamondoids has diamondoids, but it was even more challenging. Since ada-
been achieved, which will be discussed in the next section. mantane can be synthesized via the isomerization of tricyclic
The cage structures of diamondoids possess both secondary C10H16,24 the synthesis of diamantane by the aluminum halide
and tertiary carbons.14,15 The hydrogen atoms in the tertiary catalyzed isomerization of various pentacyclic C14H20 hydro-
positions of diamondoids could be substituted by functional carbons was also pursued and successfully achieved in the
groups, which provides a route to prepare a wide and selective 1960s.25 The highest yield of diamantane of ca. 60–62% was
array of diamondoid derivatives.6,16–18 These features promote obtained through the rearrangement of tetrahydro-Binor-S in a
the formation of functionalized diamondoids by design and boiling solution of carbon disulfide or cyclohexane with aluminum
enable them for applications in a wide range of areas, including bromide as the catalyst.26 Similar attempts were made to pre-
pharmaceuticals, thermal stable lubricants, microelectronics, pare higher diamondoids via carbocation rearrangement of the
optics, and polymer composites.6 corresponding cyclic hydrocarbons, and the highest diamond-
oid synthesized was anti-tetramantane (C22H28).23,27 Later on,
Dahl et al. and Shizuno et al. developed a series of innovative
2. Preparation of diamondoids synthetic methodologies, including the application of super-
critical CO2, plasma, and hot-filament-assisted chemical vapor
Adamantane was first isolated from petroleum by Landa and deposition (CVD), and eventually achieved the lab synthesis of
Machacek in 1933 using fractional distillation.11 Petroleum is still higher diamondoids such as hexamantane (C30H36).28–31 However,
the only source of adamantane in the Nature. The concentration the yields were very low. The failure to synthesize even higher
of adamantane in petroleum is extremely low (0.0001–0.03%). diamondoids is owing to the complex pathways and the large
The extremely low concentration of adamantane and the com- amount of possible intermediates during the synthetic steps.23
plicated separation process prevent the commercial production In spite of the high scientific expectation in higher diamond-
of adamantane from petroleum.19 To solve this issue, researchers oids, the difficulty in synthesizing higher diamondoids limits
explored to synthesize adamantane in the lab. Prelog and their applications.
Seiwerth achieved the first lab synthesis of adamantane in 1941, The higher diamondoids naturally occurred in petroleum32
although the yield was very low (ca. 0.16%) (Scheme 1).20,21 The could be isolated, but the isolation requires multiple steps,
total yield could be increased to ca. 6.5% after optimization of the including vacuum distillation, removal of non-diamondoid frac-
decarboxylation process,7,22,23 but this approach with multiple low tions by pyrolysis, and/or recrystallization.8 The development
yield steps still could not meet the requirement for commercial of new extraction and purification technology eventually made
production. In addition, the deacid process is a major unsatis-
factory part of this method. While this approach is not ideal for
the synthesis of adamantane, it was later adopted to synthesize
certain derivatives of adamantane.7 This situation changed
dramatically after Schleyer et al. reported their discovery to
synthesize adamantane in 1957 by the hydrogenation and Scheme 2 Schleyer’s method to synthesize adamantane.

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properly functionalized so that they can be covalently incorpo-

rated into the host systems or compatibly mixed with the host
systems. Considering the chemical reactivity order is tertiary
C–H 4 secondary C–H 4 primary C–H,37 the derivatization of
diamondoids in tertiary positions is most possible.38 Compared
to other alkanes, diamondoids are quite reactive towards radicals
and electrophilic reagents.7,39 However, their near spherical
shape and the large number of secondary and tertiary C–H bonds
with very close reactivity make the selective functionalization of
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diamondoids a rather challenging task.40

3.1 Adamantane derivatives

The smallest diamondoid, adamantane, only has two kinds
of carbon atoms, including six equivalent secondary and four
Fig. 2 Diamondoids collected from a gas field in the Gulf of Mexico. The
vial at the bottom is about 25 mm in diameter (reprinted with permission equivalent tertiary carbon atoms, which makes its selective
from Macmillan Publishers Limited).33 functionalization much easier compared to higher diamond-
oids. Many research groups7,41–46 have studied the activation
mechanisms of C–H bonds, and it was found that functional
higher diamondoids available in large quantities from the groups can be introduced to diamondoids through several sub-
petroleum by the scientists at Chevron MolecularDiamond stitution methodologies, including electrophile,47 radical,48
Technologies.33 Up to now, dodecamantane (C54H60) is the photochemical,49 as well as oxidation reactions.50 Most of these
highest diamondoid that has even been isolated from petroleum.8,34 approaches to synthesize adamantane derivatives are based on
The large amount of higher diamondoids in petroleum allows the selective functionalization of tertiary C–H bonds in ada-
them to be used as decisive indicators of natural oil cracking.35 mantane at the bridgehead positions. The common substitutes
In fact, in some natural gas production sites, ton quantities of include bromide, hydroxyl, amine, carboxyl, amide, fluoride,
diamondoids condense as crystalline solids (Fig. 2) in the flow and thiol groups.51
line, significantly compromising safety and causing costly pro- Many methods have been developed to activate the ternary
duction shutdown. Thus, diamondoids need be removed from C–H bonds of adamantane.51,52 Herein, we summarize the repre-
the production line and can be collected as by-products.33 In sentative approaches to synthesize the four most typical adaman-
spite of the difficulties in obtaining higher diamondoids, their tane derivatives: bromide, hydroxyl, amine, and carboxyl substituted
unique structures and potential promising properties still motivate adamantane.
researchers to conduct simulations of such novel molecules to Schreiner et al.52 invented a highly selective method for the
prepare for future applications.36 direct bromination of adamantane under phase-transfer con-
Different approaches to synthesize diamondoids are sum- ditions. Adamantane and tetrabromomethane were refluxed at
marized in Table 1. Currently, adamantane is mainly from the 40 1C in the presence of CH2Cl2 and 50% aqueous NaOH using
lab synthesis. Higher diamondoids are still relying on the isola- triethylbenzylammonium chloride as the phase transfer catalyst
tion from petroleum, thanks to the breakthrough by Chevron to prepare adamantyl bromide. The reaction procedures are
researchers in isolating higher diamondoids in large quantity described in Scheme 3. By choosing AlCl3 as Lewis acid catalyst
from petroleum, which are of great value for in-depth scientific and elemental bromine as bromination agent, Murray et al.53
exploration and large-scale applications. managed to prepare 1,3,5,7-tetrabromoadamantane (Scheme 4).
The hydroxyl substituted adamantane was traditionally obtained
3. Functionalization of diamondoids by the hydrolysis of halogen substituted adamantane.54 This
method is reliable but it requires a long reaction pathway with
Diamondoids are special saturated hydrocarbons with diamond- low yield. In order to overcome this shortcoming, the direct
like cage structures of sp3-hybridized carbon atoms, including hydroxylation of adamantane was explored. 1-Adamantanol was
secondary and tertiary carbon atoms. To effectively take advan- successfully prepared by the ozonation of adamantane over silica
tage of the unique properties of diamondoids, they must be gel at low reaction temperatures (Scheme 5).55,56 This simple

Table 1 A summary of preparation methods of diamondoids

Preparation method Yield Note References

Isolation from petroleum Low The highest diamondoid is dodecamantane (C54H60). 8, 11, 19, 33 and 34
Prelog’s method 6.5% Including multiple steps with a low yield. 7 and 20–23
Schleyer’s method 60–62% The highest diamondoid synthesized is anti-tetramantane (C22H28). 5 and 24–27
Miscellaneous new synthetic Low The involvement of supercritical CO2, plasma, and hot-filament-assisted 28–31
methods chemical vapor deposition (CVD). Higher diamondoids such as
hexamantane (C30H36) could be prepared.

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Scheme 3 Bromination of adamantane under phase-transfer conditions. Scheme 7 Preparation of 1,3-adamantanedicarboxylic acid.

Overall, the course to obtain adamantane derivatives depends

on the nature of substituents, catalysts, and reaction conditions.
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Among these processes, the electrophilic environment (such as

the mixtures of nitric acid, sulfuric acid, acetic acid, trifluoroacetic
acid, bromine, etc.) and electrophilic agents are required to obtain
Scheme 4 Synthesis of 1,3,5,7-tetrabromoadamantane.
the functional substituents.45,59

3.2 Higher diamondoid derivatives

The functionalizations of higher diamondoids such as tri-
amantane, tetramantane, and pentamantane were also explored
Scheme 5 Preparation of 1-adamantanol by the ozonation of adamantane
over silica gel. by both experiment and computation in the past years,40,59,60
and the synthesis of higher diamondoid derivatives was well
reviewed by Schreiner and coworkers.6 A large number of
method can synthesize 1-adamantanol with few byproducts. diamondoid derivatives with one or two functional groups
However, the solubility of ozone in organic solvents is relatively (such as –Br, –OH, –COCH3, and –COOCH3) could be prepared,
low, which limits its wide application. but the selectivity is relatively low owing to the steric effect,
The bromide and hydroxyl substituted adamantanes are the high stability, and their numerous similar C–H bonds.40,59–61
two most fundamental adamantane derivatives. Many other The derivatives from diamantane is shown in Scheme 9.40
adamantane derivatives could be prepared facilely from them Tertiary C–H bonds that are closer to the geometrical center
through various routes. For example, adamantyl amine can be of the molecule are most readily substituted by charged electro-
obtained via a four-step substitution of adamantyl bromide,53 philes. The selectivities change only slightly by varying the type
as shown in Scheme 6, while adamantanedicarboxylic acid can of electrophile, as found for diamondoid in the reactions with
be synthesized via Koch–Haff carboxylation57 of hydroxyl sub- bromine and nitrogen-containing electrophiles.
stituted adamantane (Scheme 7). The functionalizations of triamantane (Schemes 10 and 11) and
The above adamantane derivatives represent the four most tetramantane (Scheme 12) via different routes were also studied.
common adamantane derivatives. They can be easily converted Most of their derivatives substituted with mono-/di-functional
to various more sophisticated adamantane derivatives through groups (such as –OH, –COCH3, –COOCH3, and –Br etc.) amen-
classical organic reactions. able to further transformations can be prepared in high yields.
Recently, a great variety of asymmetrically substituted ada- The functionalizations of triamantane in the presence of electro-
mantane derivatives were further prepared from the readily philes gave mixtures of all possible tertiary substitution pro-
obtained various symmetric adamantane derivatives by the ducts, while the functionalizations of tetramantane are rather
selective modification of functional groups or partial desymme- selective and lead to medial substitution products in high yields.
trization of polyfunctional adamantane derivatives with identical Since the medial positions of these diamondoids are sterically
substituents.45 For instance, the trithiol functionalized adamantane hindered, the selective apical substitution is possible through
has been achieved from adamantyl bromide (Scheme 8).58 photoacetylation with triplet diacetyl, which is highly sensitive to
steric effects.
Pentamantane was found to react more effectively and
selectively with electrophiles than triamantane and tetramantane,
and it is also the highest diamondoid ever functionalized up to
now.6,60 For example, [1(2,3)4] pentamantane can not only react
selectively with neat bromine to give the 2-mono and 2,4-
disubstitution products (Scheme 13), but also could be oxidized
with nitric acid (Scheme 14) as well as go through single-
electron-transfer oxidation with high selectivities. Meanwhile,
the replacement of the functional groups in [1(2,3)4] penta-
mantane occurs without isomerization. The 2- as well as the
7-derivatives of this higher diamondoid could be obtained using
different electrophilic and/or oxidizing reagents. These findings
Scheme 6 Preparation of adamantyl amine. envision that the selective functionalization of C–H bonds on the

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Scheme 8 Synthetic route to trithiol functionalized adamantane (redrawn from ref. 58).

Scheme 9 Product ratios for the C–H substitutions of diamantine with various reagents (PTC: phase-transfer catalysis) (redrawn from ref. 40).

[1(2,3)4] pentamantane surfaces could be easily achieved under In brief, a wide diversity of diamondoid derivatives could be
mild reaction conditions with strong electrophiles-oxidizers. synthesized and then further tailored for special molecular hosts
In addition, Schreiner and coworkers synthesized extra- or various nanostructures, which could lead to widespread
ordinarily stable diamondoid dimers containing very long C–C application.5,8,9,59,60,63
bonds.61,62 The obtained dimers are thermally stable above
200 1C, which is not in line with common C–C bond length versus
bond strength correlations. They suggested that the unexpected 4. Applications of diamondoids
stability was due to the intramolecular van der Waals dispersion
interactions between the neighboring H-terminated diamond-like Their diamond-like structure warrants that diamondoids inherit
surfaces. Such dimers can also be functionalized, which further the superior properties of diamond at nanoscale, including excep-
widens the scope of possible structures for various applications. tional hardness and stiffness, high thermal stability, high chemical

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Scheme 10 Functionalizations of triamantane with electrophiles (redrawn from ref. 59).

viruses in 1964.68 This opened the door for the synthesis

and functionalization of diamondoids in medicinal chemistry.
The diamondoid structure related drugs have several pharma-
cophores69 because of their higher lipophilicity and hydro-
phobicity. They can change the absorption, distribution,
metabolism, and excretion properties of a molecule, bind to a
hydrophobic site of an enzyme and act as an inhibitor (Fig. 3),70
and disrupt the transmembrane to affect ion channels.71
The cage structures also enable them to encapsulate certain
compounds for drug delivery.64 Furthermore, diamondoids
and their derivatives are biocompatible. Therefore they can
carry a wide range of therapeutics. These functions allow diamond-
oids and their derivatives to be extensively applied for drug
development.72
In early days, the adamantane-based drugs such as amino-
adamantanes were mainly used in anti-influenza A viruses.73–75
The calling for natural products boosted the development
of pharmaceuticals from oxaadamantanes, azaadamantanes,
and heteroadamantanes for the chemotherapeutics against a
range of infections including Herpes simplex,76 Hepatitis C,77
HIV,78,79 and malaria.80,81 The adamantane-based drugs could
inhibit the reproduction of viruses by forming a hydrogen bond
with the histidine residue in the transmembrane domain
Scheme 11 Preparation of apical derivatives of triamantane via photo-
protein of viruses, thereby effectively blocking ion channels.82
acetylation (m-CPBA: 3-chloroperbenzoic acid) (redrawn from ref. 59). Some research also showed that adamantane derivatives
could act on nigrostriatal dopaminergic neurons to treat neuro-
degenerative diseases like Parkinson disease83 and Alzheimer
resistance, unique optical properties and fluorescence, and disease.84 The inhibition of enzyme properties by adamantane
excellent biocompatibility.3 These unique properties ensure is the result from a rigid scaffold, which could lead to a very
that diamondoids can be applied in many areas. Meanwhile, useful diabetes management medicine.85–87 In recent years,
diamondoids typically need be properly functionalized and adamantane derivatives have found new applications, such as
tailored towards specific applications for best performance. Up to drugs to anti-cancer, anti-acne, and weight loss.72 The unique
now, diamondoids have already found a wide range of promising features of adamantane as a useful scaffold for side chain
applications, including in pharmaceuticals, polymer composites, attachment in addition to improving the lipophilicity of
fine chemicals, nanomaterials, and optical devices.64 pharmaceuticals warrant more studies on adamantane deriva-
tives, which are still a very important subject in medicinal
4.1 Diamondoids in pharmaceuticals chemistry.
The cage-shaped structure and the wide variety of diamondoid Very recently, diamondoids and their derivatives were
derivatives allow them to be easily pursued for the conjunction explored as probes and biosensors for DNA due to the strong
with targeting molecules, such as drugs, genes, or imaging probes hydrogen bonds between the diamondoids and DNA units.88–91
for receptor-mediated delivery.65–67 Diamondoids were first intro- When the diamondoids bind with a DNA unit (such as nucleo-
duced for pharmaceutical applications when 1-aminoadamantane base), the electronic band gaps will be significantly affected
was found to be active against influenza viruses and Sendai even with weak interaction energies. As such, diamondoids can

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Scheme 12 Tertiary C–H functionalizations of tetramantane (m-CPBA: 3-chloroperbenzoic acid) (redrawn from ref. 59).

4.2 Applications in polymers

Functionalized diamondoids could provide a combination of
functionalities from the functional groups and unique properties
from diamondoid cages to create new materials. Diamondoids
exhibit high thermal stability, hardness, strength, and unique
optical properties because of their special diamond-like structure.
It was reported that the nanosized diamondoids possess better
chemical stabilities than graphite of similar size.92 These features
make them possible to be used as nanofillers and/or building
blocks (true molecular components to change the structure at the
molecular level) to prepare excellent engineering and functional
materials.46 So far, adamantane has been introduced as a
pendant group or into the backbones of polymers by radical poly-
merization, polycondensation, or coordination polymerization.93
The main purpose to incorporate adamantane into polymers is to
Scheme 13 Bromination of [1(2,3)4] pentamantane with subsequent
hydrolysis (redrawn from ref. 60).
take advantage of its high stiffness, high chemical stability, and
outstanding mechanical properties. The adamantane-containing
polymers typically exhibit a higher glass transition temperature,
clearly distinguish the regular nucleobase from the modified better solubility in organic solvents, and greater mechanical
nucleobase. properties.94
Although so far most pharmaceutical applications focus on 4.2.1 Diamondoids in polymer backbones. The incorpora-
adamantane, the promising performance of adamantane sug- tion of diamondoid units into polymer backbone is expected to
gests that certain high diamondoids should be similarly or result in polymers with higher thermal stability, increased
more effective in certain pharmaceutical applications, which chain stiffness, decreased crystallinity, and improved solubility.
motivates researchers to develop new approaches to synthesize Diamondoids as part of polymer backbones have been explored
and isolate higher diamondoids. in polyamides95 and polyimides.95,96 Polyamides are a group of

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Scheme 14 Oxidations of pentamantane with 100% nitric acid, subsequent hydrolysis, and brominations (redrawn from ref. 60).

high thermal stability. They also maintained excellent mecha-

nical properties when the temperatures were above 350 1C.
Furthermore, the introduction of diamantane skeleton could
enhance the solubility of poly(amides–imides) in N-methyl-2-
pyrrolidone, pyridine, and o-chlorophenol, which enable them
to be cast into films with high mechanical properties.
4.2.2 Diamondoids in crosslinking networks. Diamondoid
derivatives have been explored to synthesize crosslinked thermo-
sets101 and porous polymer networks (PPNs)102 because of their
cage-like structure and unique chemical properties. Thermo-
setting polymers result from pre-polymers in a soft solid or liquid
state that change irreversibly into an infusible and insoluble
Fig. 3 n-Hexanoic acid adamantyl amide deoxynojirimycin modeled into polymer network by curing. Curing can be induced by the action
the active site and a nearby hydrophobic cleft of glucocerebrosidase
of heat or appropriate radiation, or both.103 The rigid diamondoid
(reprinted with permission from the American Chemical Society).70
based monomers are widely explored to synthesize thermosets
with enhanced thermal and mechanical properties.
very important polymeric materials with widespread applica- Wei et al. explored adamantane-containing curing agents
tion due to their high durability and strength. But the lack of for epoxy.104 The resultant cured epoxy molecular composites
adequate thermal stability prohibits their application as engi- exhibited superior thermal properties as well as a good dielectric
neering materials.97 Polyimides are a group of specialty polymers performance at high frequencies. The adamantane-containing
with outstanding thermal stability, high chemical resistance, curing agents were initially synthesized from the bromide sub-
and excellent mechanical properties,96 but their insoluble and stituted adamantane via multi-step substitution.53 However, the
infusible nature limit their wide applications.96 excessive steps to synthesize the adamantane-containing curing
Adamantane derivatives have been used as co-monomers to agents hindered their wide application. Later, a new group
prepare specialty polyamides and polyimides.95,96,98–100 The of adamantane-containing epoxy molecular composites were
obtained polyamides and polyimides with adamantane groups successfully synthesized by the incorporation of adamantane
in their main chains possess a higher glass transition tempera- moieties into the epoxy pre-polymers rather than curing agents,
ture, higher thermal stability, better mechanical properties, and they were applied to prepare epoxy molecular composites
enhanced solubility, lower dielectric constants, and meanwhile using 4,4 0 -diaminodiphenyl sulfone (DDS) or dicyandiamide
remaining highly transparent. Such property improvements are (DICY) as curing agents. The obtained epoxy molecular compo-
very beneficial to widen the applications of polyamides and sites exhibited a higher glass transition temperature (223 1C),
polyimides and thus significantly enhance their value. Besides, lower moisture absorption, and a lower dielectric constant.105
the poly(amide–imide) containing alternating (amide–amide)– Recently, Ito et al.106,107 reported another group of adamantane
(imide–imide) links in the polymer backbone could also be derivatives that can be incorporated into epoxy pre-polymers.
synthesized with the addition of diamantane derivatives.98 The The adamantane-containing epoxy pre-polymers could be further
glass transition temperature of the obtained poly(amide–imide) used to prepare epoxy molecular composites, which exhibited a
with diamantane units was up to 385 1C, and they possessed high glass transition temperature (up to 221 1C), excellent optical

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characteristics (e.g., high transparency, 92% transmittance

at 400 nm), a high long-term sunlight resistance (transparency
remaining high after the cured epoxy exposed to sunlight at
60 1C for 500 hours), a high long-term heat resistance, and a
low dielectric constant. They are ideal as sealants for electronic
circuits, optical electronic members, and adhesives.
Diamondoids functionalized acetylene, diethylene, phenyl-
acetylene, diphenylacetylene or benzoxazine as thermosetting
monomers have been explored.9,94,101,108 The resulting poly-
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mers usually possess high glass transition and decomposition

temperatures and a low chain mobility owing to the hindrance
from the cage structure of diamondoids.
Adamantane-containing polymers with an adjustable porous
structure were also synthesized by the homocoupling of tetra-
hedral monomers with adamantane as the core (Fig. 4).102 The
obtained materials were insoluble in conventional solvents and
exhibited high thermal stability. The capability of trapping
gaseous molecules as well as the high chemical stability of these
polymer networks led to the applications in gas separation and
storage.102,109
4.2.3 Star polymers from diamondoid-based cores. Star
Scheme 15 Synthetic route to tetrafunctional initiators of a star polymer
polymers are a class of polymers composed of several linear with adamantane core (redrawn from ref. 111).
polymer chains connected at one point with unique rheological
and physical properties.110 Because of their highly symmetric
structure, diamondoids are ideal candidates as the core of star polymers with a monomodal molecular weight distribution
polymers. Various tetra-functionalized adamantane derivatives could be obtained, which have similar glass transition tempera-
have been explored as initiators in the synthesis of star polymers tures to the corresponding high molecular weight linear styrene
by atom transfer radical polymerization (ATRP) using monomers and acrylates.
of styrene and various acrylates (Scheme 15).111,112 Star polymers Lau et al. reported another series of star-shaped polymers
with a controlled number of arms and molecular weight, and with adamantane or diamantane as a core with multiple arms.113
relatively narrow molecular weight distribution were successfully The resultant star polymers possess low dielectric constant.
prepared by adjusting the monomer-to-initiator ratio and sol- Moreover, their dielectric constant can be tailored by varying
vent polarity. Under specific conditions, the synthesized star the overall length of the arms.113
4.2.4 Diamondoids as pendants in polymers. Polymers
with diamondoids as pendants offer high thermal stability,
excellent transparency, solubility in organic solvents, and etch-
ing resistance, as well as good processability. These polymers
are excellent candidates for high performance photoresist
materials.114,115 Recently, soluble and colorless polymers con-
taining adamantane pending groups were synthesized.116 The
unusual combination of moderately high refractive index with
low optical dispersion properties lead to the formation of
unique optical plastics.
When adamantyl groups were connected to the side chains of
certain functional polymers, such as poly( p-phenylene vinylene), the
rigid cage structure of adamantane could inhibit the aggregation
quenching of photoluminescence of the functional polymers.117,118
As such, the interaction of adamantane with functional poly-
mers can be used to tailor their functional properties such as
photoluminescence.
4.2.5 Diamondoids as regular polymer nanofillers. Their unique
Fig. 4 (a) Tetrahedral monomers and (b) the corresponding non- structure and size render diamondoids to be used as nanofillers
interpenetrated diamondoid networks of the porous polymer networks
to improve thermal and mechanical properties of polymers.
(PPNs) generated by coupling reactions. TEPM: tetrakis(4-ethynylphenyl)-
methane; TEPA: 1,3,5,7-tetrakis(4-ethynylphenyl)adamantane; TBPA: 1,3,5,7-
Diamondoids can be used as nanofillers for polypropylene and
tetrakis(4-bromophenyl)adamantane (reprinted with permission from the polycarbonate via conventional compounding.9 Interestingly,
American Chemical Society).102 the results showed that diamondoids (diamantane, triamantane,

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tetramantane, and methylated tetramantane) acted as a plasticizer derivatizations.130 Adamantane can serve as an anchoring unit
in polypropylene and increased the ductility of the resulting poly- for self-assembled monolayers58 to ensure the fixed angles
propylene composites by decreasing the yield stress and modulus of the adsorbed molecule relative to the metal surface, or as
and increasing the strain. Whereas in polycarbonate, the same tripodal anchoring points for TiO2 particles in the synthesis of
diamondoids served as anti-plasticizers and reinforcing agents, azulene chromophores.131 These could also be achieved by higher
leading to an enhanced yield stress and modulus and reduced diamondoid derivatives. The adamantane and diamantine hydra-
strain. These contradictory behaviors of diamondoids in poly- zides could be synthesized and coupled with organo-functionalized
propylene and polycarbonate could be owing to the different Sn/S clusters to form diamondoid-decorated Sn/S clusters.132 The
interactions between the diamondoids and the polymers.9 The free diamondoids as organic ligand shells provide the opportunity to
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volume in polycarbonate was probably tightly filled with the further modify and tune the properties of the Sn/S clusters, which
nanosized diamondoids. Their cage-like structure made the poly- in turn might affect their (photo)catalytic, photoluminescent, and
mer segments to be interlocked, resulting in decreased chain flexi- thermoelectric properties, their outstanding capability of Li ion
bility. However, the free volume size in polypropylene is probably storage, and conductivity.
not large enough to accommodate the rigid diamondoids. Instead, Tubular and spherical nanostructures may be obtained by
the presence of diamondoids increased the interfacial area in poly- taking advantage of self-assembly and/or coacervation of simpler
propylene, which led to an increased chain mobility. In addition, diamondoid derivatives (Fig. 5).133 For example, adamantane
the diamondoids in the polypropylene and polycarbonate compo- derivatives have rigid molecular scaffolds, which can be copoly-
sites had no adverse effects on their optical clarity. This could be merized with Keggin anions or copper/zinc cations to form porous
owing to the compatible nature of diamondoids with polypropylene metal–organic frameworks with 3D channel systems (Fig. 6).134–137
and polycarbonate, which allows diamondoids to be well dispersed Such unique nanostructures are finding more and more applica-
in nanoscale in polymer composites.9 tions in chemical industry.

4.3 Diamondoids in fine chemicals 4.5 Diamondoids in optical devices

Adamantane with lower alkyl bridgehead substituents can be The self-assembled monolayers of functional diamondoids on
used as working fluids in Rankine cycle engines, particularly in metal substrates were first found to emit electrons due to the
small vapor turbine systems119 owning to their low toxicity, high
boiling points, and exceptional thermal stability in contact with
metals. Moreover, these alkyladamantanes could be used as a
bearing lubricant in engines because of their good lubricity. In
addition to alkyladamantanes, other types of adamantane deri-
vatives, such as esters prepared from adamantanols and organic
acids have also been explored as lubricating oils. These com-
pounds usually have a high kinematic viscosity at elevated
temperatures in spite of their low pour point, and a high thermal
stability in an oxidizing atmosphere. Therefore, they are valuable
as an ingredient in high-performance lubricating oils.120,121
Besides, the adamantane derivatives as water-soluble cutting
fluids showed good antirust and antimicrobial properties.122
Adamantane derivatives are also widely used as catalysts in
various fields. Polyisobutylene and isobutylene copolymers with
novel chemical modifications could be prepared by a catalytic
system composed of a Lewis acid and adamantane deriva-
tives.123,124 Later on, the isomerization of paraffin with strong
acid catalyst and adamantane derivatives was also developed.125
It was found that adamantane acted as a hydride transfer agent
during the isomerization process.
Since the first stable carbene prepared from adamantane
derivatives by Arduengo126 in 1991, bulky diamondoid deriva-
tives have been widely adopted to stabilize carbenes and other Fig. 5 (a) A schematic presentation of the overall polyoxometalate-
similar compounds.127–129 These obtained stable carbenes encapsulating 3D polyrotaxane framework formed by molecular squares
could be widely applied as ligands in transition metal catalyzed threading on a twofold interpenetrated diamondoid skeleton. (b) Schematic
organic reactions, such as Sonogashira reaction.129 view of the helical channel after interpenetration along the a axis. (c) A space-
filling model showing two interpenetrating diamondoid units (green and blue)
4.4 Diamondoids in nanomaterials interlocked by molecular squares (red). (d) A schematic illustration of an
adamantanoid cage locked by twelve molecular squares. (e) View of the
Diamondoids are also ideal for the design of self-assembled helical nanochannel encapsulating Keggin anions (reprinted with permis-
nanoscale structures due to their unique shapes and various sion from the Royal Society of Chemistry).134

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to a drastic change in the occupied states. For instance, the

optical gap of adamantane-1-thiol is 0.6 eV lower than that of
adamantane.147
The intrinsic photoluminescence in the ultraviolet spectral
region of adamantane in gas state was discovered in 2009.148
This could be attributed to the recombination of self-trapped
excitons. The introduction of nitrogen into the crystal structure
of diamondoids will quench the luminescence. This opens a
promising field of diamondoids for nanophotonic applications
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in the ultraviolet spectral region. The photoluminescence

of diamondoids in solution,149 gas,150 and solid151 states have
been examined. All of the diamondoids were found photo-
luminescence readily, with initial excitation wavelengths ranging
from 233 to 240 nm (5.3 eV), which is ca. 1 eV lower than
any other previously studied saturated hydrocarbons.151 The
Fig. 6 Design of a decorated metal–organic framework from (a) paddle- minimum excitation energy required for photoluminescence is
wheel Cu2(OCO)4 cluster (Cu, blue; C, green; O, red) of square geometry
significantly lower for adamantane than for other saturated
(green) and (b) adamantane cluster (C, green) of tetrahedral geometry
(red). These building blocks assemble to adopt the PtS net with its vertices hydrocarbons thanks to its unusually rigid structure. In addi-
occupied by the clusters to form (c) a decorated PtS framework, where (d) open tion, the electronic properties can be tuned by chemical func-
metal sites point into the pores (same color scheme as in (a) and (b)) (reprinted tionalization of diamondoids.152–154 The electronic structures
with permission from the American Chemical Society).136 of adamantane, diamantane, triamantane, [121] tetramantane,
and [1(2,3)4] pentamantane were fully investigated by Rander
and coworkers through the variation of functional groups
negative electron affinity of the monolayer in 2007.138 In addi-
(thiol, hydroxyl, and amino) and functionalization site (apical
tion, diamondoids are unique molecular nano-materials with
and medial).152 The quantum confinement effect on the host
diamond structure and short electron mean free paths. The
cluster cage allows the highest occupied molecular orbital (HOMO)
combination of negative electron affinity and strong electron–
to be delocalized over the cage instead of being localized to a
phonon scattering enables diamondoid monolayers deposited
certain functional group located at a certain position. The
on a cathode to act as an electron monochromator, reducing the
HOMO1 ionization potential is linear with the functional
energy spread of photo-emitted electrons from the surface.139
group electronegativity except for halobenzenes. This is due
Diamondoid thin films can be prepared on noble metal (such as
to localization of the HOMO on the functional group and the
Ag(111) and Au(111)) surfaces in excellent quality by replacing
HOMO1 on the diamondoid cage. The optical absorption
hydrogen with a thiol group and using the latter as a linker to
onset of the sulfurized diamondoids can be tuned toward the
the metallic substrate.140–143 These binding energies vary with
infrared spectral region by varying the number of CQS double
diamondoid monolayer structure and thiol substitution position,
bonds at the surface of diamondoids.153 The fluorination of
consistent with different degrees of steric strain and electronic
diamondoids affects both their HOMOs and lowest unoccupied
interaction with the substrate. This led to the application of the
molecular orbitals (LUMOs). Partial fluorination may decrease
diamondoids based emitted monochromatic source of elec-
the energy of the excited state, and the LUMO becomes less
trons used in electron microscopy, electron beam lithography,
exposed to the environment around the fluorinated surface.154
and field-emission flat panel displays (Fig. 7).144–146 But the
These merits make diamondoids far more suitable for commercial-
optical properties of the diamondoids are strongly affected due
scale manufacturing and device reproduction than carbon nano-
tubes, which are heterogeneous, expensive, and hard to purify.

5. Summary and outlook

With the fascinating properties originated from their face-fused
diamond-like cage structure, diamondoids are finding more
and more high-end applications. Meanwhile, challenges still
exist. Currently, adamantane can be synthesized in lab at a low
cost,5 while high diamondoids still mainly rely on the isolation
from petroleum.33 Lab synthesis of high diamondoids remains
to be very inefficient. The derivatization of high diamondoids is
Fig. 7 Adding a single layer of diamondoid crystals to a material’s surface
also challenging in terms of selectivity, which is mainly because
greatly improves the resolution of photoelectron emission microscope of the steric effect, high stability, and their numerous similar
images (reprinted with permission from the American Institute of Physics).145 C–H bonds.40,59–61 As a result, the low cost adamantane has

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been applied in a wide range of fields, while the application of Acknowledgements

high diamondoids has been less explored, mainly owning to
their limited accessibility. The excellent properties and promising We thank Chevron MolecularDiamond Technologies for pro-
applications of adamantane in various areas suggest that higher viding samples and support for this research. This research is
diamondoids should be of similar or even higher significance. also partially sponsored by the National Science Foundation
High diamondoids are expected to be extensively investigated for (DMR-1205670) and the Air Force Office of Scientific Research
various functional applications in the coming years as they are (No. FA9550-12-1-0159). Y. Z. thanks the support by the startup
now more and more accessible. foundation for introducing talent of Nanjing University of
Derivatization has been proven to be the key to the wide- Information Science & Technology (NUIST) (2241131301102).
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spread application of diamondoids. After appropriate derivati-

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