Chemical Society Reviews

New advances in nanographene chemistry

Journal: Chemical Society Reviews

Manuscript ID: CS-REV-02-2015-000183.R1

Article Type: Review Article

Date Submitted by the Author: 22-Jun-2015

Complete List of Authors: Narita, Akimitsu; Max Planck Institute for Polymer Research, Max-Planck-
Institut fur Polymerforschung
Wang, Xiao-Ye; Max Planck Institute for Polymer Research, Max-Planck-
Institut fur Polymerforschung
Feng, Xinliang; Dresden University of Technology,
Muellen, K; Max-Planck-Institut fur Polymerforschung, Max-Planck-Institut
fur Polymerforschung
Page 1 of 28 Chemical Society Reviews

Chem Soc Rev RSCPublishing

ARTICLE

New Advances in Nanographene Chemistry

Cite this: DOI: 10.1039/x0xx00000x Akimitsu Narita,a Xiao-Ye Wang,a Xinliang Feng,b Klaus Müllen*a

Nanographenes, or extended polycyclic aromatic hydrocarbons, have been attracting renewed

and more widespread attention since the first experimental demonstration of graphene in 2004.
Received 00th January 2012, However, the atomically precise fabrication of nanographenes has thus far been achieved only
Accepted 00th January 2012
through synthetic organic chemistry. The precise synthesis of quasi-zero-dimensional
DOI: 10.1039/x0xx00000x nanographenes, i.e. graphene molecules, has witnessed rapid developments over the past few
years, and these developments can be summarized in four categories: 1) non-conventional
www.rsc.org/
methods, 2) structures incorporating seven- or eight-membered rings, 3) selective heteroatom
doping, and 4) direct edge functionalization. On the other hand, one-dimensional extension of
the graphene molecules leads to the formation of graphene nanoribbons (GNRs) with high
aspect ratios. The synthesis of structurally well-defined GNRs has been achieved by extending
nanographene synthesis to longitudinally extended polymeric systems. Access to GNRs thus
becomes possible through the solution-mediated or surface-assisted cyclodehydrogenation, or
“graphitization,” of tailor-made polyphenylene precursors. In this review, we describe recent
progress in the “bottom-up” chemical syntheses of structurally well-defined nanographenes,
namely graphene molecules and GNRs.

I. Introduction cyclodehydrogenation of hexaphenylbenzene (1) (Fig. 1), a

wide variety of π-extended PAHs were obtained by employing
After the first experimental demonstration of graphene, a tailor-made oligophenylenes as precursors.9 Such PAHs,
monolayer of graphite, by Geim and Novoselov in 2004, consisting of sp2 carbon frameworks extending over 1 nm, can
numerous research groups with different backgrounds have be regarded as the smallest possible nanographenes, or
investigated this material.1-4 Graphene has been shown to have graphene molecules.10, 17 In the last decade, the extended PAHs
a variety of exceptional properties, particularly extremely high have thus attracted renewed synthetic interest and more
charge-carrier mobilities, making it a promising material for interdisciplinary attention as structurally well-defined graphene
future nanoelectronics. However, the lack of a bandgap hinders molecules with great potential in future applications, such as in
the straightforward application of graphene in field-effect nanoelectronics, optoelectronics and spintronics.18-23
transistor (FET) devices.5 In contrast to infinite graphene with a
zero bandgap, structurally confined nanoscale graphene
segments, which are called nanographenes or graphene
quantum dots (GQDs), show non-zero bandgaps that are mainly
governed by their size and edge configurations6-8 Whereas “top-
down” methods, such as hydrothermal or lithographic “cutting”
of graphene, cannot control the resulting structure or size
distribution of the nanographenes, “bottom-up” chemical Fig. 1 Synthesis of hexa-peri-hexabenzocoronene (p-HBC 2)
synthesis provides access to monodisperse nanographenes with through intramolecular oxidative cyclodehydrogenation.
perfectly defined structures and properties.7, 9, 10
Chemical syntheses of polycyclic aromatic hydrocarbons One-dimensional extension of graphene molecules leads to
(PAHs) were pioneered by Scholl11-13 and Clar14-16 and further ribbon-shaped nanographenes with high aspect ratios, which are
developed throughout the 20th century, as summarized in our called graphene nanoribbons (GNRs).24, 25 In this article, we
previous review article.9 In particular, after highly efficient defined GNRs as nanographenes with the aspect ratios of larger
synthesis of hexa-peri-hexabenzocoronene (p-HBC, 2) was than 10, in order to clearly distinguish them from oblong-
established through the oxidative intramolecular shaped graphene molecules.17 GNRs are categorized by their

This journal is © The Royal Society of Chemistry 2013 J. Name., 2013, 00, 1-3 | 1
 Chemical Society Reviews Page 2 of 28
ARTICLE Journal Name

edge structures, as typically represented by armchair and zigzag experimentally been demonstrated, featuring semiconductor
configurations (Fig. 2). The width of the armchair and zigzag heterostructures with a straddling gap (type I) and a staggered
GNRs is generally defined by the number “N” as shown in Fig. gap (type II).38, 39
2. The width and the edge structure of the GNRs critically
define their physical properties.26 GNRs with zigzag edge
structures are predicted to show localized edge states that can
Akimitsu Narita was born in Yokohama,
be spin-polarized, which might allow their application to
Japan in 1986. He received his Bachelor’s
spintronic devices such as spin valve.27-30 On the other hand, (2008) and Master’s (2010) degrees in
armchair-edge GNRs have non-magnetic semiconducting Chemistry at the University of Tokyo under
properties with relatively larger bandgaps, which increase as the supervision of Professor Eiichi Nakamura.
their width decreases.26 The armchair GNRs are also predicted In March 2014, he obtained his Ph.D. in the
to possess high charge-carrier mobilities, which paves the way group of Professor Klaus Müllen at the Max
toward logic applications.24, 31 Planck Institute for Polymer Research (MPIP)
in Mainz. He was an Early-Stage Researcher
in the Marie-Curie Initial Training Network
(ITN) “SUPERIOR” for three years from May
2010. Beginning in August 2014, he became a project leader in the Synthetic
Chemistry Department at MPIP. His current research focuses on the bottom-
up organic synthesis of functional graphene molecules and graphene
nanoribbons.

Fig. 2 Structures of N = 9 armchair and N = 6 zigzag GNRs

with the instruction for the counting of number “N”. Xiao-Ye Wang was born in China in 1989. He
received his Bachelor’s degree in chemistry
The preparation of GNRs has primarily been conducted from Nankai University in 2009. In the same
using “top-down” methods, such as lithographic cutting of year, he joined Professor Jian Pei’s group at
graphene sheets32-34 and unzipping of carbon nanotubes.35, 36 Peking University as a graduate student and
obtained his Ph.D. degree in organic materials
FET devices based on GNRs have been demonstrated,
chemistry in July 2014. Then he joined the
suggesting their considerable potential as emerging
group of Professor Klaus Müllen at the Max
semiconductor materials. However, such “top-down” methods
Planck Institute for Polymer Research (MPIP)
are incapable of precise structural control, leading to GNRs for postdoctoral research. His research
with ill-defined widths and edge structures. To reliably tune the interests include organic electronic materials
(opto-)electronic and spintronic properties of the GNRs, it is and devices as well as bottom-up synthesis of heteroatom-doped graphene
imperative to control their structures with atomic precision, molecules and graphene nanoribbons.
which can be achieved by employing the “bottom-up” strategy
based on organic synthesis.
Xinliang Feng, after obtaining his Master's
The solution-synthesis protocol developed for the
degree in organic chemistry from Shanghai
preparation of graphene molecules can be successfully applied
Jiao Tong University in March 2004, joined
to longitudinally extended polymeric systems, which enables
the group of Prof. K. Müllen at the Max Planck
the formation of structurally well-defined GNRs, in stark Institute for Polymer Research (MPIP) and
contrast to the “top-down” fabricated GNRs with “random” obtained his PhD in April 2008. He became a
structures.17, 25 A variety of rationally designed polyphenylene group leader at MPIP in December 2007.
precursors have thus been “graphitized” through intramolecular Since June 2010, he has been a professor at
cyclodehydrogenation to provide a number of GNRs with Shanghai Jiao Tong University and became a
different widths, edge structures and heteroatom doping. distinguished group leader at MPIP in 2012. In
Furthermore, in 2010, direct growth of structurally perfect August 2014, he became a chair professor at
GNRs was achieved on metal surfaces under ultrahigh vacuum Dresden University of Technology. His current scientific interests include
graphene, two-dimensional nanomaterials, organic conjugated materials,
(UHV) conditions.37 Whereas the majority of solution-
and carbon-rich molecules and materials for electronic and energy-related
synthesized GNRs have limited solubility and thus cannot be
applications.
microscopically investigated, the surface-synthesis protocol
allowed in situ visualization of the entire GNR formation
process with atomic resolution using scanning tunneling Comprehensive reviews on the bottom-up chemical
microscopy (STM). This complementary synthetic protocol syntheses of graphene molecules9, 20, 23, 40-48 and GNRs have
under UHV conditions enabled the synthesis and direct been reported.17, 25 Thus, in this review, we focus on the most
characterization of unprecedented GNR structures that have recent advances in the field. In particular, we first discuss the
been unattainable through solution synthesis, including progress in the synthesis of graphene molecules in four aspects:
nitrogen-doped GNRs. Furthermore, GNR heterojunctions have

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 3 of 28 Chemical Society Reviews
Journal Name ARTICLE

1) newly developed, “non-conventional” synthetic methods for

graphene molecules, 2) “defective” graphene molecules, Klaus Müllen received his Ph.D. in 1972 at
involving embedded seven- or eight-membered rings, 3) the University of Basel (Professor F. Garson)
heteroatom doping of graphene molecules at defined positions after completing his Diploma in Chemistry at
and 4) chemical modification of the edges of graphene the University of Cologne (Professor E.
molecules without prior functionalization. The syntheses and Vogel) in 1969. He pursued postdoctoral
derivatizations of open-shell graphene molecules,23, 46, 49-53 research in the group of J. F. M. Oth at ETH
contorted PAHs,20 fullerene fragments,54-57 acenes,46, 58-61 Zurich, where he received his habilitation in

rylenes,62, 63 helicenes,64-68 and truxenes69, 70 have been 1977 and was appointed a Privatdozent. In
1979, he became a Professor in Organic
extensively reviewed very recently and are therefore not
Chemistry at the University of Cologne and
included in this article. In the second section, the latest
accepted an offer of a chair in Organic
developments in the bottom-up synthesis of GNRs from
Chemistry at the University of Mainz in 1983. In 1989, he became a
molecular precursors are summarized, focusing on 1) solution- scientific member of the Max Planck Society and has been the director of
mediated and 2) surface-assisted synthesis of structurally well- the Synthetic Chemistry Department at the Max Planck Institute for Polymer
defined GNRs and their characterization. Additionally, 3) Research. He served as President of the German Chemical Society for two
formation of GNR confined in carbon nanotubes is also years, beginning January 2008. His current research focuses on synthetic
described. We have recently published a personal account macromolecular chemistry, supramolecular chemistry, and materials
article, describing our own contributions over the last decade to science.
the development of the GNR synthesis.25 In the current review
article, we provide an overview of the recent advancements in
this field, featuring the results that are not covered in the In 2013, Dichtel et al. reported the synthesis of dibenzo-
previous article. fused p-HBC 6a via sequential benzannulation and
cyclodehydrogenation (Fig. 3).84 Readily accessible
di(arylethynyl)benzene derivatives 3 could be benzannulated by
II. Synthesis of graphene molecules treatment with 2-(phenylethynyl)benzaldehyde, Cu(OTf)2, and
CF3CO2H to afford precursors 4 in excellent yields, despite the
Non-conventional approaches for nanographene synthesis high steric congestion. Interestingly, the following
cyclodehydrogenation of 4a could be performed in a controlled
Over the past two decades, concise, high-yielding and scalable
manner, selectively yielding partially fused product 5a in a
synthetic methods have been developed for synthesizing
shorter reaction time, i.e., ~20 min. An extended reaction time
graphene molecules.9, 40 These methods are typically based on
of 240 min led to completely fused graphene molecule 6a (C50)
intramolecular oxidative cyclodehydrogenation, namely the
with 50 sp2 carbon atoms in the aromatic core (Fig. 3).
Scholl reaction,11, 71 of rationally designed oligophenylene
Formation of graphene molecule 6b was not observed, probably
precursors (Fig. 1). A wide variety of graphene molecules have
because of the high steric hindrance caused by the additional
thus been synthesized, with different sizes, symmetries and
tBu groups, affording partially fused 5b as the final product.
edge structures. Large oligophenylene precursors have
conventionally been prepared through cyclotrimerization of
diphenylacetylene derivatives or through a combination of
substitution and metal-catalysed coupling reactions as well as
Diels–Alder cycloaddition of alkyne and
tetraphenylcyclopentadienone derivatives.9, 40, 72, 73 The
oxidative cyclodehydrogenation can be performed with a
variety of oxidants and Lewis acids,71 including
Cu(OTf)2/AlCl3,74 FeCl3,75 MoCl5,76 2,3-dichloro-5,6-dicyano-
1,4-benzoquinone (DDQ)/Brønsted or Lewis acid,77 and
[bis(trifluoroacetoxy)iodo]benzene (PIFA)/BF3·Et2O.78
Nevertheless, the scopes of these synthetic methods have
been limited by several factors, including incomplete
“graphitization,”79 chlorination74 and unexpected structural
rearrangements80-83 during the Scholl reaction. Furthermore,
oligophenylene precursors, corresponding to the desired
graphene molecules, were often inaccessible in the
Fig. 3 Syntheses of partially fused PAHs 5 and fully fused
conventional manner. This renders it essential to develop new, graphene molecule 6a via benzannulation and
“non-conventional” methods for the synthesis of nanographene, cyclodehydrogenation.
which enables preparation of graphene molecules with
tailorable (opto-)electronic properties.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 3
 Chemical Society Reviews Page 4 of 28
ARTICLE Journal Name

Partially fused PAHs 5 have distinct non-planar structures without further formation of aryne 16. Under the presence of
with a theoretically estimated dihedral torsion angle of 56°. CsF and a catalytic amount of [Pd2(dba)3] (dba =
Notably, PAH 5b exhibited enhanced visible absorption dibenzylideneacetone), triflate 15 was successfully converted to
compared with that of fully fused graphene molecule 6a, with PAH 17 through the palladium-catalysed cyclotrimerization of
an optical gap of 2.32 eV derived from its UV–Vis absorption the in situ generated aryne 16. PAH 17 could be sublimed onto
spectrum. This value was smaller than the 2.53 eV optical gap a bilayer of NaCl on Cu(111), and high-resolution atomic force
of fully fused molecule 6a, suggesting that the structural non- microscopy (AFM) and STM analyses revealed its molecular
planarity has an effect on the (opto-)electronic properties of structure and orbitals with atomic resolution.
graphene molecules.85
This synthetic protocol can be applied to other
(arylethynyl)benzene derivatives,86 providing potential access
to previously unavailable graphene molecules, including
contorted species with open bonds at selective positions.
Furthermore, the benzannulation strategy has proven to be also
effective for poly(phenylene ethynylene)s to yield sterically
congested polymers with diarylnaphthalene units,87 which
might serve as precursors for GNRs.
In 2014, Wei and his colleagues developed an elegant two-
step synthetic route for obtaining C3 symmetrically substituted
hexa-cata-hexabenzocoronenes (c-HBCs) 9, which had been
unobtainable through existing methods (Fig. 4).88 Starting from
1,3,5-tri(bromomethyl)-benzene (7), 1,3,5-tribenzylbenzene
derivatives (TBBs, 8) were prepared via three-fold Suzuki
coupling with phenylboronic acid derivatives. Subsequently,
TBBs 8 were reacted with three equivalents of benzaldehyde
building blocks under the presence of FeCl3 and acetic
anhydride as oxidant/Lewis acid and dehydrating agent,
respectively. Remarkably, c-HBCs 9 could be obtained in one
Fig. 4 Facile two-step synthetic route for obtaining C3
pot, where a sequence of Friedel–Crafts hydroarylation, symmetrical c-HBC 9, TBTTC 10 and graphene molecule 11.
intramolecular alkylation, dehydrogenative aromatization, and
intramolecular cyclodehydrogenation occurred. By using
thienaldehyde instead of benzaldehyde, this synthetic method
provided access to sym-tribenzotetrathieno-coronenes (TBTTC,
10), which had been sought after previous syntheses of
dibenzotetrathienocoronene (DBTTC)89, 90
and
hexathienocoronene (HTC)91, 92 (see Fig. 12). Moreover,
phenanthraldehyde could be employed in this protocol to obtain
unprecedented C3 symmetrical graphene molecule 11 with 72
sp2 carbon atoms in the aromatic core (Fig. 4).
The use of aryne chemistry is also a convenient method for
the synthesis of PAHs, involving [4+2] or [2+2+2]
cycloadditions.45, 93 In particular, Perez, Guitian, Peña, and co-
workers have demonstrated that the palladium-catalysed
cyclotrimerization of arynes enables very efficient preparation
of triphenylene94 and a variety of its extended derivatives,93 Fig. 5 Synthesis of PAH 17 (C78) through two-step
including hexabenzo[a,c,g,i,m,o]triphenylene (C42),95 cycloadditions of arynes.
hexabenzo[a,c,k,m,u,w]trinaphthylene (C54)96 and
hexabenzo[a,c,o,q,c1,e1]trianthrycene (C66).97 By further Although syntheses via cyclotrimerization of arynes often
advancing this method, they recently developed a simple require multi-step preparation of aryne precursors,
synthetic protocol for C3 symmetrical PAH 17 (C78), starting cyclotrimerization of o-dibromoarenes through Yamamoto
from bisbenzyne precursor 12 and perylene (14) (Fig. 5).98 coupling can serve as a complementary approach.99 The
Perylene (14) was first reacted with aryne 13, which was Yamamoto conditions can also tolerate silyl groups, which are
generated in situ from 12 by treatment with CsF, providing unstable in the presence of fluoride used for the in situ
triflate 15 via a Diels–Alder cycloaddition. With careful generation of arynes. In 2014, Bunz and co-workers employed
optimization of the reaction temperature and solvent, triflate 15 this approach of Yamamoto coupling to synthesize
could be selectively precipitated from the reaction mixture, unprecedented large starphenes, i.e., trideca-starphene 19 (C54)

4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 5 of 28 Chemical Society Reviews
Journal Name ARTICLE

and hexadeca-starphenes 21 (C66) from dibromotetracene 18 halogenated phenacenes, which can be directly used for further
and dibromopentacene 20, respectively (Fig. 6).100 coupling reactions or dehalogenated by simple treatment with
Triisopropylsilyl (TIPS)-ethynyl groups were successfully n-butyllithium.103, 106, 107, 109, 110 Although the platinum-
installed on starphenes 19 and 21, which made them highly catalysed cycloaromatization of precursor 27 was unsuccessful,
soluble in organic solvents, thereby allowing their the use of ICl allowed conversion of 27 to [4]phenacene 28,
characterization using NMR and X-ray crystallography. The followed by graphitization to graphene molecule 29 (C52) (Fig.
optical gaps of starphenes 19 and 21 were estimated from their 7).106 Further details regarding such metal-catalysed or metal-
UV–Vis absorption spectra to be 2.29 and 1.76 eV, mediated reactions can be found in recent review articles.56, 101-
103, 111, 112
respectively, which were approximately 0.2 eV smaller than
those of linear precursors 18 and 20.

Fig. 6 Syntheses of trideca-starphene 19 and hexadeca-

starphenes 21 from dibromotetracene 18 and dibromopentacene
20, respectively, through Yamamoto coupling.

In addition to the palladium-catalysed [2+2+2] cycloaddition

Fig. 7 Syntheses of PAH 23 through Al2O3-mediated C–H
and nickel-mediated Yamamoto coupling, other metal-catalysed
arylation and of graphene molecules 26 and 29 via platinum-
reactions are also very useful for constructing graphene
catalysed and ICl-mediated cycloaromatization, respectively.
molecules.56, 101-103 For instance, palladium-catalysed C–H
arylation has been widely used for the preparation of non- Graphene molecules with seven- or eight-membered rings
planar PAHs incorporating five-membered rings,56 and
palladium-catalysed double cross coupling can extend 1,2- As two-dimensionally confined structures of graphene,
dibromoarenes with 9-stannafluorenes, leading to various nanographenes, in principle, consist of only six-membered
triphenylene derivatives.101 Amsharov et al. developed an rings. However, microscopy studies have revealed that
Al2O3-mediated C–H arylation of fluoroarenes via C–F graphene also contains rings of other sizes, including five-,
activation, allowing the unconventional use of C–F bonds for seven- and eight-membered rings, as defects, particularly at the
the intramolecular aryl–aryl coupling of PAHs, for example, to grain boundaries of graphene sheets grown by chemical vapour
obtain PAH 23 (C46) from fluoroarene 22 (Fig. 7).104, 105 deposition (CVD).113-117 Therefore, extended PAHs containing
Furthermore, ruthenium- or platinum-catalysed electrophilic non-six-membered rings can indeed be considered as graphene
cycloaromatization of ortho-alkynylated biaryls is a versatile molecules, which allow model studies of “defective” graphene
method to form phenanthrene structures, as represented by the and may also find applications in (opto-)electronics. PAHs with
conversion of precursor 24 to [6]phenacene 25, which enabled five-membered rings have been extensively synthesized and
the synthesis of graphene molecule 26 (C52) through investigated as fullerene fragments and their derivatives
subsequent cyclodehydrogenation (Fig. 7).56, 106-108 Here, ICl- following the pioneering works by Scott et al.44, 54-57, 102, 118
mediated cycloaromatization of ortho-alkynylated biaryls can However, there are only scarce examples of graphene
serve as a metal-free alternative method for obtaining molecules containing seven- or eight-membered rings.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 5
 Chemical Society Reviews Page 6 of 28
ARTICLE Journal Name

PAHs with a central n-membered ring that is completely in common organic solvents, and, astonishingly, graphene
surrounded by fused benzenoid rings are called [n]circulenes, molecule 42b with tert-butyl groups could be dissolved even in
based on the definition by Wynberg.119-121 According to this hexane. Graphene molecule 42 was comprehensively
definition, corannulene and coronene are [5]circulene and characterized spectroscopically, and X-ray crystallographic
[6]circulene, respectively. Moreover, [7]circulene and analysis revealed that 42 possessed a unique double-concave
[8]circulene can be regarded as graphene molecules containing structure. Although the oxidative cyclodehydrogenation has
seven- and eight-membered rings, respectively. [7]Circulene been employed almost exclusively for preparing of planar
was first synthesized by Yamamoto and Nakazaki et al. in graphene molecules, the above-mentioned recent results clearly
1983,122 followed by [7.7]circulene in 1991, which incorporated demonstrated that it is also a very powerful method for
two seven-membered rings.123 Nevertheless, graphene synthesizing non-planar graphene molecules.
molecules with embedded seven-membered rings, other than
the circulenes, had remained elusive. C6H13O OC 6H13 C 6H13 O OC 6H13
FeCl 3
In 2012, Miao et al. reported a curved graphene molecule 31
with an embedded seven-membered ring (Fig. 8), which is π- C6H13O OC 6H13
62%
C 6H13 O OC 6H13
isoelectronic to p-HBC 2 (C42).124 The synthesis consisted of
the oxidative cyclodehydrogenation of hexaphenylbenzene- 30 31

based precursor 30, which was prepared via the Diels–Alder

cycloaddition of a tetraphenylcyclopentadienone derivative and
an aryne generated in situ from 10-bromo-5H- RO OR RO OR
DDQ
dibenzo[a,d]cycloheptene (Fig. 8). Introduction of alkoxyl
CF3SO 3H
groups at ortho or para positions to the reaction sites was found RO OR RO OR

to be crucial for achieving the complete cyclodehydrogenation

process; otherwise, a mixture of inseparable products was O
obtained. In a follow-up report in 2015, they synthesized two
RO OR 33a: R = n-octyl 34a: R = n-octyl
new aromatic saddles, C70H26 (34a,b) and C70H30 (36a,b), with 33b: R = n-hexyl 34b: R = n-hexyl

two embedded heptagons.125 The synthesis was carried out

RO OR
through saddle-shaped diketones (32a,b) as the key precursors,
bearing two tropone subunits incorporated in the well-known O RO OR RO OR

framework of p-HBC. These aromatic saddles 34 and 36 were 32a: R = n-octyl DDQ
32b: R = n-hexyl
successfully obtained by π-extension on the carbonyl groups of RO OR
CF3SO 3H RO OR

precursor 32 and further oxidative cyclodehydrogenation. The

saddle-shaped structures of these graphene molecules were
unambiguously characterized by single-crystal X-ray analysis.
35a: R = n-octyl 36a: R = n-octyl
In 2013, Durola and co-workers conducted oxidative 35b: R = n-hexyl 36b: R = n-hexyl

cyclodehydrogenation of sterically congested precursor 37 and tBu

tBu
tBu
unexpectedly obtained graphene molecule 38 (C66) as a major
product (Fig. 8), whose structure was confirmed by X-ray FeCl 3

crystallographic analysis.126 Although the expected C3 tBu 73%

symmetric graphene molecule was not obtained due to the tBu
rearrangement during the Scholl reaction, graphene molecule tBu

38 is one of the rare examples with an embedded seven- 38

37

membered ring. This result provides further insights into the Fig. 8 Syntheses of graphene molecules 31, 34, 36 and 38
rearrangements or migration of aryl groups in the Scholl with embedded seven-membered rings through
reaction, which still remain elusive. cyclodehydrogenation.
In 2013, Scott, Itami, and co-workers made major progress,
achieving concise, two-step synthesis of grossly warped Whereas [7]circulene was synthesized in 1983,122
graphene molecule 42 (C80) with five embedded seven- [8]circulene had not been achieved until recently, probably
membered rings and one five-membered ring at the centre (Fig. because of its highly strained and instable structure.130 The first
9).127 Starting from corannulene (39), precursors 40 and 41 synthetic attempt was reported in 1976 by Wennerström et al.,
were obtained by palladium-catalysed direct C–H arylation but photocyclisation of [2,2](3,6)phenanthrenophanediene in
with arylboroxins, using o-chloranil as an oxidant.128, 129 the final step did not afford the [8]circulene, presumably owing
Remarkably, the intramolecular cyclisation of precursors 40 to the high steric demand.131 In 2013, Wu and co-workers
and 41 efficiently provided grossly warped graphene molecule reported the first synthesis of peri-substituted [8]circulene 44
42 in good yields, overcoming the high steric demand to form through four-fold palladium-catalysed annulations of tetraiodo-
five distorted seven-membered rings. Because of its highly non- substituted tetraphenylene 43 with diarylethynes (Fig. 10).132
planar structure, graphene molecule 42 showed good solubility

6 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 7 of 28 Chemical Society Reviews
Journal Name ARTICLE

Octaaryl-[8]circulene 44 could be obtained in remarkable 60– tetrabenzocyclooctane precursor 49. Interestingly, Diels–Alder
75% yields, corresponding to ~88–93% for each annulation reactions using 2,5-diphenylfuran or 2,5-diphenylthiophene
step, allowing the preparation of several hundred milligrams of dioxide instead of 48 required higher temperatures, resulting in
44. [8]Circulene 44 was unambiguously characterized through the decomposition of dibenzocyclooctadiyne 47. This result
NMR and X-ray crystallographic analyses, which revealed its indicated the high potential of thiophene-1-oxides as the dienes
non-planar saddle-like structure. in the Diels–Alder reactions although they have rarely been
used for this purpose. Subsequently, the palladium-catalysed
C–H arylation of precursor 49 afforded tetrabenzo[8]circulene
Tris(o-biphenylyl)boroxin 46a in 24% yield. Because of its full benzenoid structure,
Pd(OAc) 2
o-chloranil tetrabenzo[8]circulene 46 exhibited high stability, in contrast to
the parent [8]circulene, without any deterioration under ambient
21%
conditions over five months or at 100 °C for 24 h.
39

40 R R R R
Ar Ar
Tris[p-(t-butyl)phenyl]boroxin mixture of regioisomers
Pd(OAc) 2, o-chloranil I I Ar Ar
23% DDQ, TfOH R R Ar Ar R R
50%
R R Pd(OAc)2, NaOAc R R
tBu tBu R R I I nBu4NCl, DMF Ar Ar

R R Ar Ar
60–75% R R
tBu tBu R R
43a: R = Me 44a: R = Me, Ar = 4-MeC6H4
43b: R = OMe 44b: R = OMe, Ar = 3,5-Me2C6H3
FeCl 3 mixture of regioisomers 44c: R = OMe, Ar = 4-MeC6H4
tBu tBu R R
62%
R R R R
R R R R
tBu tBu R R Cu(OTf)2, AlCl3, CS2
(R = H), 7%
tBu tBu R R
41 42a: R = H FeCl3,CH2Cl2
42b: R = tBu
(R = Me), 35%
Fig. 9 Synthesis of grossly warped graphene molecules 42 R R R R
R R R R
through C–H arylation and cyclodehydrogenation of 45a: R = H 46a: R = H
corannulene (39). 45b: R = Me 46b: R = Me
DBU, DMA
microwave
Later in the same year, Sakamoto and Suzuki reported the O 24%
synthesis of tetrabenzo[8]circulene 46 via oxidative S Cl Cl

cyclodehydrogenation (Fig. 10).133 Cycloocta-o,p,o,p,o,p,o,p- Cl Cl

48
phenylene 45a was prepared as a precursor through Suzuki
toluene
coupling of o-terphenylboronic ester and o-dibromobenzene.
47
14%
Precursor 45a was subsequently subjected to Cl Cl
cyclodehydrogenation with Cu(OTf)2 and AlCl3, affording 49

tetrabenzo[8]circulene 46a in 7% yield. Because the Fig. 10 Syntheses of [8]circulene 44 through palladium-
intermolecular coupling to form a dimeric byproduct was found catalysed annulation and of tetrabenzo[8]circulene 46 through
to be one reason for the low yield, precursor 45b with eight oxidative cyclodehydrogenation or a sequence of Diels–Alder
methyl groups was subsequently prepared. Oxidative cycloaddition and palladium-catalysed C–H arylation. DBU:
cyclodehydrogenation of precursor 45b with FeCl3 provided 1,8-diaza-bicycloundec-7-ene; DMA: N,N-dimethylacetamide.
octamethyl-tetrabenzo[8]circulene 46b in an improved (35%)
yield. X-ray crystallographic analysis of tetrabenzo[8]circulene Apart from the [8]circulene derivatives, there are scarce
46a showed its deep saddle structure with two S4-symmetrical examples of graphene molecules with embedded eight-
conformers, which were twisted from the D2d-symmetrical membered rings. In 2014, our group reported the synthesis of
ground-state structure revealed by density functional theory biphenylene-based PAH 51, incorporating one eight-membered
(DFT) calculations. This observation provided evidence for the and one four-membered rings, through oxidative
theoretically predicted pseudorotation of tetrabenzo[8]circulene cyclodehydrogenation of octaarylbiphenylene 50 (Fig. 11).135
46 via a non-planar transition state. The cyclodehydrogenation did not proceed further, probably
At almost the same time, Whalley and co-workers developed because of the high steric demand, selectively providing PAH
another synthetic route for tetrabenzo[8]circulene 46a based on 51 in 90% yield. The UV–Vis absorption and emission spectra
a sequence of Diels–Alder cycloaddition and palladium- of PAH 51 revealed its relatively large optical bandgap of ~2.8
catalysed C–H arylation (Fig. 10).134 In the first step, eV and an emission at 552 nm, respectively. A large Stokes
dibenzocyclooctadiyne 47 was subjected to two-fold Diels– shift of 4000 cm–1 was observed, which indicated partial
Alder reactions with 2,5-diarylthiophene-1-oxide 48 to afford planarization of PAH 51 in the excited state.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 7
 Chemical Society Reviews Page 8 of 28
ARTICLE Journal Name

possibility of thermally activated T1 to S1 intersystem

crossing.144

R1 R1 R 2O OR2 R 2O OR2
R1 R1 R1 R1 R1 R1
N
R1 R1 R1 N N R1 R1 R1
N N N N

N N R1 N N R1 N N
R1 R1 R1 R1
N N
R1 R1 R1 R1 R1 R1
R1 R1 R1 R1 R 2O OR2
52 53 54
Fig. 11 Synthesis of biphenylene-based PAH 51, containing
R 2O OR2 Ar1 Ar1 Ar1 Ar1
one eight-membered ring and one four-membered ring, via R1 R1 Ar1 Ar1 Ar1
Ar1
cyclodehydrogenation of octaarylbiphenylene 50. N Ar1 Ar1 N Ar1
R1 N N R1 Ar1 N N N
N
R 2O OR2 Ar2 Ar2 Ar2
Heteroatom-doped graphene molecules Ar1 N N N N
N N Ar1 Ar1 N Ar1
Ar1
Heteroatom-doped graphene is a new class of materials that OR2 OR 2 Ar1 Ar1 Ar1
R1 R1 Ar1 Ar1 Ar1 Ar1
possess properties and functions different from those of the 55 56 57
parent graphene.136-138 However, the heteroatom doping of R4
N OR6
R3 R3
graphene sheets with precise structural control has not been R5 OMe
OMe S
tBu N
achieved, hindering studies of structure-property relationships N X
S
X
N MeO R5
at the atomic or molecular level. By contrast, bottom-up N R 6O N
N MeO
organic synthesis can provide structurally defined heteroatom- 60
tBu N R5 N OMe
doped graphene fragments with perfect control not only of the OMe tBu
R3 R3
59
size, periphery and substituent, but also of the doping R4
58a: R 3 = H, R 4 = tBu
concentration and position. Although a wide variety of 58b: R 3 = R 4 = OMe
tBu
N
heteroatom-doped structures have been developed for small
N N N
PAHs, until recently there had been only a few examples for N
expanded PAHs.41, 60, 139-141
As typical examples of nitrogen (N)-doped graphene tBu 61 tBu 62 63 tBu
C8H17
molecules, we developed a series of pyrrole-fused azacoronenes
C6F 5
52–55 (Fig. 12), together with Takase, Nishinaga and their N
N N
N
colleagues, through the oxidative cyclodehydrogenation of N N
N
corresponding hexaarylbenzenes.142, 143 These PAHs N
C6F 5
N

incorporating electron-rich pyrrole-type nitrogens exhibited up 65 C8H17

tBu 64 66
to four reversible oxidation processes in the electrochemical
Fig. 12 Representative examples of N-doped PAHs. R1: H or
measurements. They were also easily oxidized by chemical
4-trifluoromethylphenyl; R2: methyl, n-butyl or n-dodecyl; Ar1:
oxidants, e.g., SbCl5, to generate radical cations and dications.
p-butoxyphenyl; Ar2: p-nitrophenyl; R5: phenyl, 4-
The stepwise replacement of pyrrole rings with
methoxyphenyl, 4-bromophenyl, methyl, hexyl, etc.; R6: 2-
dialkoxybenzenes significantly changed their optical and
ethylhexyl or 2-decyltetradecyl; X: H, Br, trimethylstannyl, etc.
electronic properties in both neutral and oxidized states. For
example, the emission colours of these compounds changed
In 2014, Stępień and co-workers explored a new type of
from red to green as the number of pyrrole rings decreased
expanded hexapyrrolohexaazacoronenes 56 and 57 with
from six (52) to three (55) (Fig. 12). The quinoidal resonance
interrupted peripheral conjugation, by introducing saturated
structures of 522+ and 532+ stabilized these dication species,
methylene bridges (Fig. 12).145 These molecules can also be
inducing higher oxidation potentials in the next step from
regarded as the first examples of N-doped graphene molecules
dication to trication states, which was not observed for 542+ and
with embedded seven-membered rings. The synthesis was
552+. In the dication states, hexaazacoronene 522+ and
conducted from substituted hexapyrrolylbenzenes in a two-step
pentaazacoronene 532+ exhibited a closed-shell character. On
condensation–aromatization sequence, i.e., a Lewis acid-
the other hand, an open-shell character was theoretically
catalysed bridging with p-nitrobenzaldehyde followed by
predicted for tetraazacoronene 542+ and triazacoronene 552+.
oxidative cyclodehydrogenation. Notably, the peripheral
The introduction of dialkoxybenzenes instead of pyrrole rings
bridges could be aromatized through oxidative dehydrogenation,
prohibited the charge/spin delocalization in the π-system, which
and subsequent nucleophilic additions proceeded in a perfectly
resulted in “weakly interacting” spins with an open-shell
stereospecific manner, allowing functionalization with a variety
character. In addition, small S1–T1 energy gaps (<0.36 eV) were
of substituents. These new azacoronenes with methylene
observed in this family of compounds, which is very interesting,
bridges exhibited easily accessible higher oxidation states.
particularly in the field of molecular photonics, considering the
Remarkably, contrary to the cases of 52–55, a tetracationic

8 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 9 of 28 Chemical Society Reviews
Journal Name ARTICLE

species 574+ could be chemically generated by oxidation with Furthermore, generation of 61 at a high temperature
SbCl5, which was presumably enabled by the disrupted provided self-dimerization product 63 in 51% yield, which
peripheral conjugation. might serve as a precursor for an unprecedented p-HBC with
In contrast to the electron-rich pyrrole-fused graphene two nitrogen atoms inside the aromatic core.151 In 2015, Ito and
molecules, incorporation of imine-type nitrogen in the PAH Nozaki et al. achieved an unprecedented synthesis of 6b2-
framework by fusing pyridine or pyrimidine rings creates azapentabenzo[bc,ef,hi,kl,no]corannulene 64 based on the 1,3-
electron-deficient N-doped graphene molecules. In 2002, dipolar cycloaddition of azomethine ylide 61 with 2,2',6-
Draper et al. reported the first example of such a molecule, trichlorodiphenylacetylene, followed by three-fold Pd-catalysed
namely, N-doped p-HBC 58a (Fig. 12), through the oxidative cyclisation (Fig. 12).154 N-doped corannulene derivative 64 is a
dehydrogenation of a corresponding pyrimidine-incorporated rare example of bowl-shaped PAHs with heteroatom doping
hexaarylbenzene precursor.146 N-doped p-HBC 58a served as a inside the aromatic framework, and demonstrated distinctly
versatile ligand for metal (e.g., PdII and RuII) complexes.147 The different structural and opto-electronic properties compared to
photophysical properties of N-doped p-HBC 58a were the parent corannulene. These results indicate a high potential
demonstrated to be effectively modulated by metal coordination. of the azomethine ylide chemistry based on 61 and its
In 2014, Draper et al. performed methoxy functionalization derivatives for exploring a new class of N-doped PAHs, which
on the periphery to obtain N-doped p-HBC 58b and found that cannot be accessed by other synthetic methods.
the cyclodehydrogenation process was promoted by In 2015, Anand and co-workers reported a metal-assisted
incorporating electron-donating methoxy groups.148 The cyclodimerization of doubly N-confused dipyrrin into
photophysical and electronic properties were profoundly azaheptalene 65.155 Single-crystal X-ray analysis revealed the
affected by the methoxy substitution. Furthermore, the X-ray planar structure of 65 with two embedded seven-membered
crystal structure of 58b revealed that the intermolecular rings. In the same year, Gryko and co-workers reported a
hydrogen bonds involving methoxy groups and nitrogen atoms photochemical direct arylation method to convert
assist the molecules to arrange in a head-to-tail manner in the phenanthro[9,10-d]-imidazole derivatives with 2-halogenoaryl
columnar stack. substituent into phenanthro[9′,10′:4,5]imidazo[1,2-f]-
The family of PAHs doped with imine-type nitrogens also phenanthridines, such as N-doped PAH 66, in high yields.156
includes azacoronene derivatives. For example, 1,5,9- This reaction occurred without a need of any photosensitizer or
triazacoronene 59 was synthesized by Wei et al. with a base, presumably through the formation of a radical anion as a
threefold Pictet-Spengler reaction as the key step (Fig. 12).149 critical step.
These compounds exhibited an electron-deficient nature Thiophene-fused PAHs have been extensively explored
compared to the all-carbon analogue. Recently, Liu et al. because of their wide applications in organic electronic
reported a novel thiophene-fused azacoronene 60, featuring two devices.157-159 From the synthetic point of view, several
imine-type nitrogens on the skeleton.150 Azacoronene 60 beautiful thiophene-annulated structures have also been
bearing bromo or trimethylstannyl groups could be further developed, such as octathio[8]circulene (“sulflower”),160
functionalized through Stille coupling, which also allowed tetrathienoteropyrene161 and thiophene-fused heptalenes162 and
incorporation of 60 into conjugated polymers. Azacoronene 60 coranulenes.163 Here we focus on π-extended PAHs, mainly
with two fused thiophene rings was relatively electron-rich and consisting of hexagonal rings, as sulphur (S)-doped graphene
showed hole mobilities of up to 0.028 cm2 V–1 s–1 in FET molecules. We synthesized a tribenzothiophene-fused p-HBC
devices. Furthermore, conjugated polymers incorporating 67 as the first example of such molecules with embedded
azacoronene 60 functioned as the donor material in organic thiophene rings (Fig. 13).164 In 2011, Draper et al. reported p-
photovoltaic devices, which exhibited a high open-circuit HBC 68 with an embedded thiophene ring via oxidative
voltage of 0.89 V and a power conversion efficiency (PCE) of cyclodehydrogenation.165 They could also obtain a dimer of S-
4.8%. doped p-HBC 68 through intermolecular oxidative coupling at
In 2014, we reported the synthesis of dibenzo-9a- the thiophene rings, which showed concentration-dependent
azaphenalene (61), which features a N-doped zigzag-edge optical properties governed by the relative orientation between
structure (Fig. 12).151 With 61 as the basic unit, its dimer 62 the two S-doped HBC planes.
was also successfully synthesized, suggesting the possibility of In addition to these examples based on p-HBC, Nuckolls et
further lateral extension toward N-doped zigzag-edge GNRs. al. developed a synthesis of dibenzotetrathienocoronene
Dibenzoazaphenalenes 61 and 62 are featured with azomethine (DBTTC) 69, a thiophene-fused c-HBC analogue (Fig. 13).89, 90
ylide structures, showing extremely high chemical reactivity, The aromatic core of 69 could self-assemble into a columnar
and thus they were generated only under inert conditions. superstructure, which merged into a three-dimensional network
Azomethine ylide 61 could be employed in 1,3-dipolar of supramolecular cables. When the acceptor C60 was
cycloaddition reactions with various dipolarophiles, providing a evaporated into this network, a nanostructured p-n bulk
unique pathway to N-doped PAHs with fused pyrrole rings.152 heterojunction was formed, providing a PCE of 1.9% in a solar
Nozaki et al. found that 61 can also react with fullerene C60 to cell device. Furthermore, solution-processed photovoltaic
form an adduct.153 devices of DBTTC 69 and phenyl-C70-butyric acid methyl ester
(PC70BM) showed a PCE of 2.7%, where a supramolecular

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 9
 Chemical Society Reviews Page 10 of 28
ARTICLE Journal Name

complex between 69 and PC70BM was demonstrated to play an significant contribution to the molecular orbitals, which
important role in the charge separation process.166 induced broad absorption over the entire visible region as well
More recently, we synthesized a class of fully thiophene- as fluorescence extending to the NIR region. They also
annulated coronenes, namely, hexathienocoronenes (HTCs) 70 demonstrated syntheses of extended triphenylborane 73171 and
and 71, which are stronger electron donors with higher HOMO internally B-doped PAH 74 with two fused-thiophene rings and
levels compared to DBTTC 69 (Fig. 13).91 Based on single- an embedded seven-membered ring (Fig. 14).169 In 2015,
crystal X-ray analysis, HTC 71 adopted an almost planar Wagner and co-workers reported a modular synthesis of B-
conformation due to the relatively weak steric congestion of the doped PAHs, including 7,14-diborabisanthene 75.172 The
six peripheral thiophene rings. Columnar stacking was also replacement of the two meso carbons of bisanthene with B
observed for 71, providing suitable charge transport channels. atoms turned a near-infrared dye into an efficient blue
The skeleton of HTC 71 was later used to construct a gemini- fluorescent compound (75) with a high quantum yield of 78%.
type amphiphile, which yielded various ordered assemblies in Another approach to incorporating B atoms in π-conjugated
solution, at the liquid-solid interface and in the solid state.92 systems consists of replacing the common CC unit with its
Remarkably, the blend of amphiphile 71 and PC60BM exhibited isoelectronic BN unit, which has led to a new class of
photoconductive properties with a large on/off ratio of 6 × 104. compounds that have properties distinct from those of their
The synthesis of TBTTC 10 by Wei et al. (Fig. 4) further carbon analogues but maintain structural similarity.139-141 The
enriched the diversity of the family of thiophene-fused c-HBC dipolar BN unit has a significant impact on the molecular
analogues as described above. orbitals, intermolecular interactions and photophysical and
redox properties of the π-system, providing a unique strategy
S
S
for molecular engineering.173-178 In 2015, Pei et al. reviewed the
R R history and progress of BN-substituted PAHs, and proposed
S that suitable BN-containing PAHs could be used as precursors
for the bottom-up construction of BN-doped graphenes with
well-defined structures.139 Here we mainly focus on large BN-
R R
embedded π-skeletons, which are model compounds and
S
potential precursors for BN-doped graphenes.
R
68
67

R R R R R R
S S S S
S S

S S

S S

S S
S S S S
R R R R R R
DBTTC 69 HTC 70 HTC 71

Fig. 13 Examples of S-doped graphene molecules. R

represents hydrogen or alkyl substituents.

Boron (B) atoms have also been incorporated in PAHs,

resulting in intriguing properties. Generally, B-containing
compounds are unstable toward moisture and oxygen owing to
the intrinsic high reactivity of B atoms. Bulky substituents are
thus typically required to kinetically protect the Lewis acidic B
centre.167 However, the steric bulkiness prevents intermolecular
interactions in the solid state, which is detrimental to charge
transport properties. Yamaguchi et al. proposed a new strategy
for stabilizing tri-coordinated boron-containing π-systems by
“structural constraint.”168, 169 The planarized skeleton was
highly stable and could be handled without any special
precautions. Using this strategy, Yamaguchi et al. achieved the
Fig. 14 Examples of B- and BN-doped PAHs. Mes: mesityl;
synthesis of the first example of B-doped graphene molecule 72,
X: H, Br or Ph; R: n-butyl or n-hexyl.
which contained two boron atoms inside the carbon framework
(Fig. 14).170 The key step of the synthesis consisted of oxidative
Piers and co-workers developed a series of BN-embedded
cyclodehydrogenation using FeCl3. The boron atoms had a
PAHs, such as BN-substituted pyrene (76)179 and

10 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 11 of 28 Chemical Society Reviews
Journal Name ARTICLE

dibenzo[g,p]chrysene (77),180 which raised modern research reactivity of the P centre, e.g., through transformations into
interest in this field. In 2011, Hatakeyama, Seki and Nakamura thiooxophosphole, oxophosphole and phospholiums, allowing
et al. reported the first step toward extended BN-doped PAHs, fine-tuning of its energy gap.
demonstrating the synthesis of BN-doped hexabenzotetracene
78 through tandem intramolecular electrophilic arene borylation
(Fig. 14).178 In 2014, Pei et al. pioneered a straightforward
strategy toward BN-doped graphene molecules by employing
azaacenes as a platform for constructing large BN-embedded π-
systems.181 As a proof of concept, π-extended BN
heterocoronene derivatives 79 with two BN units were
synthesized from 6,13-dihydro-6,13-diazapentacene (Fig. 14).
The ring-closure step involved the efficient construction of two Fig. 15 Examples of P-doped PAHs.
B–N bonds and four B–C bonds through an electrophilic
borylation method. The introduction of BN units in the skeleton
had a pronounced influence on its electronic properties and Direct edge functionalization of graphene molecules
molecular geometry. The molecules showed a tendency to pack
Although the physical properties of graphene molecules are
into a columnar structure, which facilitated the formation of
governed primarily by their aromatic core structures,
one-dimensional micro-ribbons through solution-processed
substituents at their peripheries also play a major role.21, 192 For
self-assembly. FET devices based on the micro-ribbons
example, alkyl chains as the substituents can change the
exhibited hole mobilities of up to 0.23 cm2 V–1 s–1.
solubility and the phase-forming and self-assembly behaviour
Photoconductive properties were also observed, indicating the
of graphene molecules, which in turn affect, e.g., the
potential application of BN-embedded graphene molecules for
performance of (opto-)electronic devices fabricated with them.
organic photovoltaics. This work also paved a way toward the
By introducing electron-donating or electron-withdrawing
fabrication of BN-doped graphenes based on the π-extension of
groups as substituents, it is also possible to directly modify
BN-containing PAHs.
their (opto-)electronic properties. Moreover, substitution with
In 2015, Pei et al. and Zhang et al. almost simultaneously
chemically reactive substituents such as halogens allows further
reported their independent syntheses of C3-symmetric BN
structural functionalization of graphene molecules.
heterocoronene 80 with three BN units (Fig. 14).182, 183 The
Nevertheless, the introduction of different substituents at the
planar and aromatic structure of 80 was clearly revealed by the
edges of graphene molecules often requires tedious synthetic
single-crystal X-ray analysis and NMR spectroscopy. The UV–
input, starting from the modification of basic building blocks.
Vis absorption and emission spectra of 80 showed blue-shifted
Moreover, the scope of substituents that can be introduced is
peaks compared to those of a similarly alkoxylated coronene,184
often limited because of their instability or incompatibility
demonstrating an increase of the energy gap as a result of the
under the reaction conditions. For example, the oxidative
BN doping.182 The phenyl groups at the B positions were
cyclodehydrogenation could be hampered by increased steric
selectively replaced with hydroxy groups in wet organic
hindrance or modification of the electronic energy levels by the
solvents, which further increased the energy gap.183 In the same
substitution. Therefore, direct edge functionalization of already
year, Bettinger et al. successfully constructed B3N3-doped p-
formed graphene molecules is desirable but yet remains
HBC 81 by thermolysis of a tris(2-biphenylyl)borazine
underexplored.
precursor at 550 °C.185 The structure was verified by mass
Halogens on the edges of graphene molecules can be
spectrometry and infrared and solid-state NMR spectroscopy.
converted to cyano groups,193, 194 and be used for various metal-
B3N3-doped p-HBC 81 was also sublimated onto Au(111)
catalysed coupling reactions, such as Sonogashira, Suzuki and
surfaces for STM characterization, which showed that this
Buchwald coupling with terminal alkynes,195, 196 boronic
molecule lies flat on the surface in a 2D pattern.
acids/esters197 and primary/secondary amines,193, 194
Phosphorus (P)-doped graphene molecules are another very
respectively. Moreover, alkoxy and ester groups can also be
interesting class of compounds, considering the remarkable
introduced via palladium-catalysed coupling reactions.193
(opto-)electronic properties of phosphole-based materials.186-188
Nevertheless, these methods require the prior introduction of
Nevertheless, there are only a few examples of PAHs with
halogens.
embedded P atoms. In 2011, Hatakeyama and Nakamura et al.
In 2013, we reported a very efficient edge chlorination
reported the synthesis of P-doped PAH 82 through the tandem
protocol for extended graphene molecules that consists simply
phospha-Friedel–Crafts reaction, demonstrating the extended π-
of refluxing with an excess amount of iodine monochloride and
conjugation over the entire molecule (Fig. 15).189 In 2014, they
a catalytic amount of AlCl3 in carbon tetrachloride.198
further extended the synthesis and obtained P-doped PAH 83
Syntheses of a series of perchlorinated graphene molecules, as
with high structural distortion.190 On the other hand, Réau and
represented by 85–89, have thus been achieved in excellent
co-workers succeeded in the preparation of planar P-doped
yields, with the number of sp2 carbon atoms ranging from 42 to
PAH 84 via photocyclisation.191 Notably, the (opto-)electronic
222 (Fig. 16). The electronic energy levels of the graphene
properties of PAH 84 could be starkly modified by utilizing the

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 11
 Chemical Society Reviews Page 12 of 28
ARTICLE Journal Name

molecules were lowered by the edge chlorination, providing an

unprecedented class of n-type graphene molecules that function
as electron transporting materials. The bandgaps of the
graphene molecules were also reduced compared to their parent
molecules. Furthermore, the planarity of the graphene
molecules was distorted by the steric hindrance between the
chloro groups densely attached on the peripheral positions,
which drastically enhanced their solubility. The increased
solubility enabled their liquid-phase characterizations, solution Fig. 17 Synthesis of sulphur-annulated graphene molecules 90
processing and even X-ray single-crystal analysis of and 91 through the thiolation of perchlorinated HBC 85. DMI:
unprecedentedly large PAH molecules, including 88 with 96 1,3-dimethyl-2-imidazolidinone.
sp2 carbons. Interestingly, the crystal structure of 88 showed
that the “gulf” position199 of graphene molecules was not Shinokubo and co-workers applied the iridium-catalysed
chlorinated (Fig. 16), most likely due to the steric hindrance direct borylation reaction201 to p-HBC derivatives, such as 92,
caused by the two chloro groups installed on the neighbouring providing diborylated p-HBC 93 (Fig. 18).202, 203 Starting from
positions. diborylated p-HBC 93, they synthesized a variety of p-HBC
The chloro groups installed at the peripheries of the derivatives.202, 204 First, diborylated p-HBC 93 was oxidized to
graphene molecules can be employed for further chemical dihydroxy-p-HBC 94 and then methylated to afford dimethoxy-
functionalizations. Based on perchlorinated HBC 85, we very p-HBC 95. p-HBC bistriflate 96 was also prepared from
recently demonstrated edge-thiolation of graphene molecule, dihydroxy-p-HBC 94, which could be employed for various
which provided unprecedented tri-sulphur-annulated HBC palladium-catalysed coupling reactions. Alkynyl-substituted p-
(TSHBC) 90 and di-sulphur-annulated HBC (DSHBC) 91 HBC 97 and diamino-p-HBC 98 could thus be obtained through
densely decorated with arylthio groups (Fig. 17).200 X-ray Sonogashira coupling and Buchwald–Hartwig amination,
single-crystal analysis unambiguously demonstrated the respectively. Furthermore, p-HBC bistriflate 96 could also be
structures of HBCs 90 and 91 with embedded thiophene rings, cyanated to dicyano-p-HBC 99 based on a cyanation protocol
which constitute a new class of S-doped graphene molecules reported by Takagi et al.205 The photophysical properties of the
with S-annulated peripheries. The UV–Vis absorption spectrum p-HBC derivatives were strongly affected by their substituents,
of TSHBC 90 showed a significant red shift of 100 nm which demonstrated the significance of such direct edge
compared to that of parent p-HBC 2, indicating a decrease in functionalization protocols to easily introduce electron-
the optical bandgap of 0.5 eV. Electrochemical studies of donating and electron-withdrawing groups.
TSHBC 90 revealed three reversible reduction processes, which The direct edge functionalization is of great importance not
could be tuned by introducing electron-donating or electron- only for the modification of the peripheral substituents, but also
withdrawing groups on the arylthio substituents. for the construction of novel aromatic structures, as elegantly
demonstrated by Scott, Itami et al. with the two-step synthesis
Cl Cl Cl
Cl Cl Cl Cl Cl Cl
Cl
Cl Cl
Cl
Cl Cl
Cl of grossly warped graphene molecule 42 from corannulene (39)
Cl Cl
Cl Cl Cl Cl
Cl Cl (Fig. 9).127 The direct palladium-catalysed C–H arylation with
Cl Cl Cl Cl

Cl Cl Cl
Cl Cl o-chloranil as the oxidant was shown to occur exclusively at the
Cl
Cl Cl Cl Cl
Cl Cl K-regions of PAHs, which allowed their selective two-step π-
Cl Cl
Cl Cl Cl
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl extension, for instance, from phenanthrene to
Cl Cl Cl
C 42Cl18 (85) C 48Cl18 (86)
C60Cl 22 (87) dibenzo[g,p]chrysene.129 Moreover, Itami et al. very recently
Cl made a further advancement, realising direct one-step π-
Cl Cl
Cl
Cl Cl
Cl
extension of PAHs at the K-regions through palladium-
Cl Cl
Cl Cl
Cl catalysed double C–H activation.206 Additionally, Scott et al.
Cl Cl Cl Cl

Cl
Cl Cl
Cl
Cl Cl also reported iridium-catalysed five-fold borylation of
Cl Cl
"gulf" Cl Cl corannulene (39) to afford 1,3,5,7,9-pentakis(BPin)corannulene
position Cl Cl
Cl Cl
Cl Cl
(BPin = (pinacolato)boron), which provided facile access to a
Cl Cl
Cl Cl defined molecular fragment of [5,5]nanotube207 and the third
Cl Cl
Cl Cl
Cl Cl synthetic route to graphene molecule 42 via a single isomer of
Cl Cl
Cl Cl
precursor 40.127 Scott et al. also pioneered π-extension at the
Cl Cl Cl Cl
Cl Cl Cl Cl Cl Cl bay regions of perylene and bisanthene through the Diels–Alder
Cl Cl Cl Cl
C96Cl 27H 3 (88)
Cl
Cl Cl
Cl reaction.208, 209 Notably, the bay regions of such PAHs can
Cl Cl
Cl Cl function as the dienophiles and undergo cycloadditions with
Cl
C 222Cl 42 (89) activated ethylenes and acetylenes, as well as with arynes,
Fig. 16 Examples of edge-chlorinated graphene molecules. providing facile access to PAHs extended at the bay
positions.210-213

12 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 13 of 28 Chemical Society Reviews
Journal Name ARTICLE

ultraviolet spectroscopy, as well as through investigation of

BPin OH
structurally related model compounds.
Ar Ar
[{Ir(OMe)(cod)2]
Ar Ar Ar Ar In 1993, Scherf et al. reported a fully conjugated ladder-type
dtbpy, (BPin)2 oxone
polymer, called “angular polyacene,” that consisted only of six-
membered rings; this polymer can be considered one of the
Ar Ar Ar Ar Ar Ar
narrowest possible GNRs with a defined structure.217, 218 The
BPin OH
p-HBC 92
p-HBC 93 Tf2O p-HBC 94
synthesis was carried out through carbonyl olefination of
pyridine
MeI functionalized poly(para-phenylene) with B2S3217, 218 or
tBu K2CO3
through McMurry coupling.219 In 1994, Swager et al.
OTf OMe
synthesized the same ladder-type polymer with different
tBu
Ar Ar
[PdCl2(PPh3)2]
Ar Ar Ar Ar substituents through intramolecular electrophilic substitution
CuI, DBU
with arylethynyl groups via the formation of a vinyl cations
Ar Ar Ar Ar Ar Ar
under an acidic condition.220
H2NAr KCN In an attempt to prepare wider ladder-type polymers, or
OTf [Pd2(dba)3]—CH2Cl2 OMe
[Pd2(dba)3]—CH2Cl2
DPPF, Zn p-HBC 95
GNRs, we have extended the nanographene synthesis based on
BINAP, Cs2CO3 p-HBC 96
tBu
p-HBC 97
oxidative cyclodehydrogenation to polymeric systems, using
NHAr CN
longitudinally elongated polyphenylenes as precursors.25
Ar Ar Ar Ar Beginning in 2001, syntheses of structurally defined GNRs
were attempted using A2B2-type Diels–Alder polymerization
Ar Ar Ar Ar
for the preparation of polyphenylene precursors.221, 222
However, this approach was unsuccessful because of the
NHAr CN
p-HBC 98 p-HBC 99
formation of numerous structural isomers during the
polymerization step, resulting in a mixture of randomly kinked
Fig. 18 Derivatizations of p-HBC via iridium-catalysed direct GNRs. Since 2000, Osuka et al. have developed the synthesis
edge borylation. Ar: mesityl; cod: cycloocta-l,5-diene; dtbpy: of one-dimensionally extended porphyrin tapes, achieving
4,4'-di-tert-butyl-2,2'-bipyridyl; BPin: (pinacolato)boron; DBU: porphyrin 24-er in 2009 as the longest to date.223-226 Although
1,8-diazabicyclo[5.4.0]undec-7-ene; dba: dibenzylideneacetone; the porphyrin tapes are neither PAHs nor GNRs by definition,
BINAP: 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl; DPPF: they are exquisite examples of structurally well-defined
1,1'-diphenylphosphinoferrocene. aromatic nanoribbons.

Through A2B2-type Suzuki polymerization. The previous

III. Synthesis of graphene nanoribbon synthetic attempts that employed A2B2-type Diels–Alder
polymerization did not afford structurally defined GNRs due to
Solution-mediated synthesis of graphene nanoribbons the structural isomerization. Thus, we have next performed the
Whereas graphene molecules that are smaller than 5 nm can not synthesis of GNRs through A2B2-type Suzuki polymerization,
bridge two electrodes in electronic devices, one-dimensionally which does not induce structural isomerization. In 2008,
extended GNRs allows fabrication of transistors based on single structurally well-defined and straight N = 9 armchair GNRs
GNR strands, which is essential for the logic applications.24, 31 were obtained for the first time using this polymerization
Bottom-up synthetic efforts toward GNRs date back to 1970, method.227 With bulky alkyl chains at the peripheral positions,
when Stille et al. reported the first attempt to synthesize a fully the GNRs were highly dispersible in organic solvents, allowing
conjugated ladder-type polymer consisting of hexagonal and their liquid-phase processing and visualization on a graphite
pentagonal aromatic rings.214 Although such aromatic ladder- surface by STM. Nevertheless, the length of the observed
type polymers were not recognized as “GNRs” at that time, GNRs was only up to ~12 nm, which prompted us to develop
their aromatic, ribbon-like structures can indeed be viewed as other synthetic protocols for obtaining longer GNRs, namely,
GNRs with defined defects, i.e., five-membered rings. by enhancing the degree of polymerization during the synthesis
Nevertheless, the ladder-type polymer obtained by Stille et al. of the polyphenylene precursors.
was almost insoluble due to strong π-π stacking interactions, The low polymerization efficiency was considered to be due
leaving the structural characterization inconclusive at that to the high steric hindrance between the coupling monomers
time.215 This solubility problem was solved in 1994 by Schlüter and to the high rigidity of the poly(p-phenylene) backbone
et al., who introduced flexible alkyl loops that wrapped the structure. We have thus devised the use of a kinked and more
aromatic polymers.215, 216 Thanks to the increased solubility and flexible poly(o-phenylene-p-phenylene) 102 as a GNR
improved synthetic procedure, the formation of an aromatic precursor.228 Polyphenylene precursor 102 was synthesized
ladder-type polymer could be unambiguously confirmed by through a microwave-assisted A2B2-type Suzuki polymerization
elemental analysis, solid-state 13C NMR and transmission of o-dibromobenzenes 100 and benzene-1,4-diboronic ester 101
(Fig. 19). Size exclusion chromatography (SEC) analysis of the
resulting polyphenylene 102b with dodecyl chains indicated a

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 13
 Chemical Society Reviews Page 14 of 28
ARTICLE Journal Name

number-average molecular weight (Mn) of 9,900 g/mol and a In 2013, Jo and his colleagues extended the synthesis of
polydispersity index (PDI) of 1.4 against a poly(styrene) (PS) GNR 103 by using naphthalene diboronic ester 104 and
standard. This Mn value corresponded to the average length of anthracene diboronic ester 107 in place of benzene diboronic
approximately 25 nm for planarized GNR 103b, suggesting the ester 101 to obtain wider GNRs 106 and 109, respectively (Fig.
advantage of such kinked polyphenylene backbones for the 19).230 Whereas the degree of cyclodehydrogenation was
synthesis of longer GNRs via the A2B2-type Suzuki demonstrated to be 100% for precursor 102 based on the
polymerization. relative intensities of aromatic protons in NMR spectra, the
Noted that the “molecular weights” from the SEC analyses values for precursors 105 and 108 were determined to be 78%
are only approximate values estimated based on available and 75%, respectively. This result suggested that
calibration curves of existing polymer standards and do not cyclodehydrogenation has limited efficiency for precursors
represent the absolute molecular weights, which can be containing naphthalene or anthracene units. Notably, thin-film
measured using laser light scattering experiments.229 FET devices fabricated with GNRs 103c, 106 and 109 all
Nevertheless, because the SEC molecular weights are useful for exhibited ambipolar transport properties. Wider GNRs showed
roughly comparing the sizes of polymers with similar higher FET performances, and GNR 109 displayed the highest
structures, we include the SEC data in this article solely for this hole and electron mobilities of 3.25 × 10–2 and 7.11 × 10–2
purpose. cm2/V·s, respectively, probably as a result of the most extended
π-conjugation.

Fig. 19 Synthesis of GNRs 103, 106 and 109 with various widths based on A2B2-type Suzuki polymerizations. BPin:
(pinacolato)boron.

In addition to modifying the width and edge structure, N-doped GNRs 110 and 111 (Fig. 20) was indicated by the
heteroatom doping of aromatic frameworks is another NMR analysis. Notably, a higher degree of N-doping reduced
promising method for drastically modifying the electronic the hole mobilities of the GNRs while increasing the electron
properties of GNRs, as discussed above for graphene mobilities. This result demonstrated that the charge-transfer
molecules. Jo et al. conducted N-doping of GNRs using a behaviour of the GNRs could be tuned from ambipolar to n-
mixture of dibromobenzene 100 and 2,3-dibromo-5,6-bis- type by N-doping. GNR 111 with the highest degree of N-
dodecyloxy-pyrazine in the Suzuki polymerization with doping exhibited the highest electron mobility of 1.02 × 10–1
naphthalene diboronic ester 104.231 By changing the mixing cm2/V·s, which was two orders of magnitude higher than that
ratio between the dibromopyrazine and dibromobenzene 100, of non-doped GNR 106. Moreover, the threshold voltages of
GNR precursors with different degrees of N-doping could be the GNRs varied from +20 V for non-doped GNR 106 to –6 V
obtained. Upon cyclodehydrogenation, 100% conversion into for N-doped GNR 111.

14 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 15 of 28 Chemical Society Reviews
Journal Name ARTICLE

The UV–Vis absorption spectrum of GNR 114 revealed its

relatively smaller optical bandgap of ~1.4 eV, which was in line
with the DFT calculation.

Through AA-type Yamamoto polymerization. Although the

use of the A2B2-type Suzuki polymerization enabled the
preparation of various structurally defined GNRs, the
longitudinal extensions of these GNRs, i.e., molecular weights
of the polyphenylene precursors, were limited. This restriction
Fig. 20 Structures of N-doped GNRs 110 and 111 prepared was possibly a result of the inefficiency of the A2B2-type
through A2B2-type Suzuki polymerizations. Suzuki polymerization and/or the necessity of two different
monomers causing stoichiometry problems.233, 234 The
We have also synthesized GNR 114 featuring a unique heterogeneous biphasic conditions of the Suzuki polymerization
“necklace-like” structure through the A2B2-type Suzuki might also have a detrimental effect. Therefore, AA-type
polymerization of 4,4'-dibromobiphenyl-based precursor 112 Yamamoto polymerization was considered to be more
and benzene-1,4-diboronic ester 101 (Fig. 21).232 advantageous because this method requires only one
Polyphenylene precursor 113 was obtained with a weight- dihalogenated monomer and is thus free of the stoichiometry
average molecular weight (Mw) of 6,900 g/mol and a PDI of 1.7 problem. Moreover, the Yamamoto coupling is also known to
according to SEC analysis against a PS standard. MALDI-TOF be highly efficient in sterically hindered systems,235, 236 which is
MS analysis of precursor 113 displayed mass peaks up to m/z = important for the preparation of sterically congested GNR
17,000, corresponding to 113 with ten repeating units, which precursors.
converted to GNR 114 with the length of approximately 13 nm.

Fig. 21 Synthesis of “necklace-like” GNR 114 through A2B2-type Suzuki polymerization of naphthalene-based monomer 112
and laterally extended GNRs 117 and 120 through AA-type Yamamoto polymerizations of p-terphenyl-based monomer 115 and o-
terphenyl-based monomer 118, respectively. Obtained GNR 120 was rather short and mixed with shorter graphene molecules.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 15
 Chemical Society Reviews Page 16 of 28
ARTICLE Journal Name

In 2012, we synthesized laterally extended GNR 117 sublimed and integrated into FET devices through vapour-
through the AA-type Yamamoto polymerization of phase transport deposition, showing better on-off ratio
dichlorinated monomer 115 (Fig. 21).237 Notably, the compared to those processed from a liquid phase.239
Yamamoto polymerization of 115 proceeded very efficiently, In 2014, Sinitskii et al. reported the gram-scale synthesis
yielding polyphenylene precursor 116 with an Mw of 52,000 and comprehensive characterizations of chevron-type GNR 123
g/mol, an Mn of 44,000 g/mol and a PDI of 1.2 according to through the AA-type Yamamoto polymerization of 6,11-
SEC analysis against a PS standard, which were clearly higher dibromo-1,2,3,4-tetraphenyltriphenylene (121)240 and
than the molecular weights achieved using the A2B2-type subsequent cyclodehydrogenation (Fig. 22).241 GNR 123 had
Suzuki polymerization. The laterally extended GNR 117 with previously been prepared in our group using the solution
an estimated width of 1.54–1.98 nm featured a significantly synthesis242 as well as the surface-assisted method37 as will be
lowered optical bandgap of approximately 1.1 eV with broad discussed in the next section. Nevertheless, they have
absorption into the near-infrared region of the optical spectrum. demonstrated the well defined structure of the solution
We have next attempted a synthesis of even wider GNR 120 synthesized GNR 123 for the first time using STM under UHV
with an estimated width of ~2.1 nm, corresponding to N = 18 conditions, clearly observing the planarization of three-
armchair GNR, by employing monomer 118 (Fig. 21).238 While dimensional precursor 122 into planar GNR 123.241 UV–Vis
monomer 115 with a dichlorinated p-terphenyl backbone absorption measurements of GNR 123 in a dispersion revealed
structure yielded GNR 117 with the same width as 115, its optical bandgap of approximately 1.6 eV.243
monomer 118 with a dichlorinated o-terphenyl backbone led to Moreover, using the same synthetic strategy, Sinitskii et al.
GNR 120, which was twice as wide as the monomer. However, conducted a solution synthesis of N-doped, chevron-type GNR
the AA-type Yamamoto polymerization of monomer 118 126, starting from 5-(6,11-dibromo-1,3,4-triphenyltriphenylen-
afforded polyphenylene precursor 119 with a relatively low Mw 2-yl)pyrimidine (124) (Fig. 22).244 STM analysis revealed a
of 10,000 g/mol, an Mn of 7,200 g/mol and a PDI of 1.4 based defined structure of GNR 126 similar to that of GNR 123, and
on SEC analysis against a PS standard, presumably because of energy-dispersive X-ray (EDX) and X-ray photoelectron
high steric hindrance during the polymerization. The observed spectroscopy (XPS) measurements corroborated the successful
optical bandgap of GNR 120 was approximately 1.6 eV. These N-doping. The optical bandgap of GNR 126 was derived from
results indicated that the obtained GNR 120 was rather short, its UV–Vis absorption spectrum to be approximately 1.6 eV,
and mixed with oblong-shaped graphene molecules, based on which was the same as that in its non-doped analogue, GNR
the definition given in the introduction. Additionally, such 123.
relatively large graphene molecules could be successfully

Fig. 22 Synthesis of pristine and N-doped chevron-type GNRs 123 and 126, respectively, based on AA-type Yamamoto
polymerizations. N-doped precursor 125 and GNR 126 are obtained as mixtures of structural isomers.

Through AB-type Diels–Alder polymerization. The use of However, such metal-catalysed coupling reactions are generally
the AA-type Yamamoto and A2B2-type Suzuki polymerization limited by the use of expensive catalysts and relatively low
methods has enabled bottom-up synthesis of structurally molecular weights, in most cases leading to GNRs shorter than
defined GNRs with different widths and edge structures, 50 nm. Turning back to the traditional polyphenylene synthesis,
reaching a length of >100 nm with chevron-type GNR 123.241 the Diels–Alder reaction is still appealing because it

16 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 17 of 28 Chemical Society Reviews
Journal Name ARTICLE

reproducibly offers Mw values higher than 100,000 g/mol based the cyclodehydrogenation of 128 is hindered by the steric
on SEC analyses in many systems.221, 245, 246 Moreover, no repulsion between benzene rings and bulky alkyl chains,
catalyst or additive is necessary for the Diels–Alder reaction, ensuring the non-kinked and uniform structure of the resulting
which is highly advantageous for larger-scale syntheses. GNR 129.
In 2014, we have for the first time reported an AB-type The AB-type Diels–Alder polymerization of monomer 127a
Diels–Alder polymerization to prepare GNR 129 with a “cove- afforded precursor 128a with a markedly high Mw of 640,000
type” edge structure, which simultaneously enabled g/mol, an Mn of 340,000 g/mol and a PDI of 1.9 based on SEC
unprecedentedly high longitudinal extension over 600 nm (Fig. analysis, thereby proving the remarkably high efficiency of this
23).229 King et al. has coined a term “gulf” for such edge polymerization method. The UV–Vis absorption spectrum of
configuration in 2008,199 but we use the term “cove-type” for GNR 129 revealed a large optical bandgap of ~1.9 eV, which
these GNRs in this review, following older literature.9, 40, 81 In was in excellent agreement with theoretical predictions.247 The
this approach, tetraphenylcyclopentadienone-based monomer edge chlorination method developed for the graphene
127 was rationally designed such that all the structural isomers molecules (Fig. 16) also proved to be applicable for GNR 129c
of the resulting precursor 128 would lead to a single, straight to afford chlorinated GNR 130, which demonstrated lowered
GNR 129 with an estimated width of 0.69–1.13 nm (Fig. 23).229 optical bandgap as expected by the theory (Fig. 24).198, 247
Furthermore, C–C bond formation at undesired positions during

Fig. 23 Synthesis of GNRs 129 and 133 through AB-type Diels–Alder polymerization of monomers 127 and 131, respectively.

Transistor devices could be fabricated by directly depositing

metal electrodes on such GNR strands, which exhibited good
electrical conduction through the isolated GNRs.249, 251
In 2014, we have achieved lateral extension of GNR 129 by
using monomer 131 with four additional benzene rings at the
peripheries of monomer 127 (Fig. 23a).252 Notably, the Diels–
Alder polymerization of monomer 131 led to polyphenylene
precursor 132 with a high Mw of 550,000 g/mol, an Mn of
Fig. 24 Edge chlorination of GNR 129c to GNR 130. 150,000 g/mol and a PDI of 3.8 based on SEC analysis against
the PS standard, which was comparable to the highest
Furthermore, deposition of isolated strands of GNR 129a molecular weight values obtained for the narrower precursor
was achieved by immersing a functionalized Si/SiO2 substrate 128. The resulting GNR 132 exhibited broad absorption profile
in a diluted dispersion of 129a, demonstrating that the GNRs into the NIR region with a lowered optical bandgap of
extended over 600 nm.249, 250 By treating the Si/SiO2 substrate approximately 1.2 eV, which was in good agreement with the
with silane derivatives with different hydrophobicities, it is DFT-calculated bandgap.253 Ultrafast terahertz (THz)
possible to control the density of the deposited GNRs.250 photoconductivity measurements demonstrated excellent

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 17
 Chemical Society Reviews Page 18 of 28
ARTICLE Journal Name

intrinsic mobility of GNR 132, similar to that of the narrower armchair GNR 136 in a similar manner (Fig. 25a), which could
GNR 129a.248 Moreover, the broad absorption of GNR 132 clearly be visualized by in situ high-resolution STM (Fig.
enabled spectroscopic characterizations at a wider range of 25b).37 STS measurements revealed that the electronic bandgap
wavelengths, as represented by Raman and pump-probe THz of GNR 136 is 2.3 eV on the Au(111) surfaces261 in agreement
photoconductivity analyses, which is indispensable for in-depth with the theoretical estimation.262 Following our report, many
studies on the fundamental properties of such GNR structures. other research groups have successfully prepared and studied
atomically precise GNR 136. Grill et al. measured the
Surface-assisted synthesis of graphene nanoribbons conductivity of a single nanoribbon of 136 using an STM
Synthesis under UHV conditions. A number of structurally pulling technique.263 Liljeroth and Swart et al. obtained
defined GNRs with different widths, edge structures and atomically resolved AFM images of GNR 136 and
heteroatom doping have been successfully synthesized based on demonstrated creation of a single GNR-Au bond by removing
the solution-mediated method, as discussed in the previous one hydrogen atom with a local high voltage pulse.264
section. However, microscopic visualization with atomic Moreover, Huang and Wee et al. showed that N = 7 GNR 136
resolution and in-depth physical characterizations of such could be fused in parallel with neighbouring nanoribbons on
GNRs have remained a challenge because of their strong Ag(111) surfaces, leading to the formation of N = 14 and 21
aggregation tendency and the difficulty of placing isolated armchair GNRs.265
strands of such GNRs on a surface without any contamination. Spatially aligned GNRs can be grown by using stepped
In 2010, in collaboration with Fasel and his colleagues, we have Au(788) surfaces, in contrast to the formation of randomly
developed a complementary approach to this solution synthesis, oriented GNRs on Au(111) surfaces. This spatial alignment
i.e., direct growth of GNRs on metal surfaces under UHV allowed the detailed investigation of the occupied electronic
conditions.37 Using this surface-assisted method, atomically states of the GNRs through angle-resolved UV photoemission
precise structures of the resulting GNRs can be clearly spectroscopy (ARUPS)260, 261 Such spatially well-aligned GNRs
observed in situ using the state-of-the-art high-resolution STM. also enabled studies of their optical properties on the metal
This method combines the surface-assisted coupling of aryl surfaces using reflectance difference spectroscopy (RDS),
halides developed for the preparation of molecular wires254 and revealing the strong anisotropy of GNR 136 and its optical
covalently bonded networks255-257 with surface-catalysed bandgap of 2.1 eV.262 The difference between this optical
cyclodehydrogenation, which we demonstrated for the bandgap and the DFT-calculated electronic bandgap of 3.7 eV
synthesis of a defined triangular PAH, tribenzo[a,g,m]coronene, could be explained by the exciton binding energy. On the other
from a cyclic polyphenylene, cyclohexa-o-p-o-p-o-p- hand, the electronic bandgap observed by the STS analyses was
phenylene.258 In the surface synthesis of the GNRs, the revealed to be reduced by the polarization of the metallic
corresponding polyphenylene precursors are first fabricated substrates.262
from rationally designed, dihalogenated monomers through the In 2014, Han and Asao et al. demonstrated that the same
surface-assisted coupling of aryl halides. Here, biradical monomer 134 undergoes intermolecular cyclodehydrogenation
intermediates are generated through carbon–halogen bond at different configurations on a Cu(111) surface, leading to an
cleavage upon thermal treatment of the monomer on the unprecedented formation of chiral-edge (3,1)-GNR 137 with
surface, followed by radical polymerization. Subsequently, the atomic precision (Fig. 25a and c).266 In contrast to the GNR
polyphenylene precursors are “planarized” and “graphitized” synthesis on a Au(111) surface, where the biradical
through surface-catalysed cyclodehydrogenation by annealing intermediates can freely diffuse, the monomers on a Cu(111)
at higher temperatures to produce the desired GNRs. All these surface are demobilized even at elevated temperatures and the
processes can be monitored using high-resolution STM, cyclodehydrogenation occurs only inside preassembled
allowing full control over each synthetic step. domains. Thus the resulting GNRs are distributed along distinct
With Fasel and his colleagues, we have performed the first directions relative to the Cu(111) atomic rows, which is
attempt for the surface-assisted synthesis of GNRs using 6,11- predetermined by the self-assembly of the monomers.
dibromo-1,2,3,4-tetraphenyltriphenylene (121) as the starting By extending dibromobianthryl monomer 134 to 2,2'-
monomer,37 which we had previously synthesized as the di[(1,1'-biphenyl)-2-yl]]-10,10'-dibromo-9,9'-bianthracene
monomer of blue-light-emitting polymer 122240 as well as for (138) with two extra biphenyl units at the peripheries, Fischer,
the solution synthesis of chevron-type GNR 123259 (Fig. 22). Crommie, and co-workers achieved a selective synthesis of
Remarkably, monomer 121 could be polymerized to laterally extended N = 13 armchair GNR 140 on a Au(111)
polyphenylene 122 upon sublimation onto a Au(111) surface surface and visualized its atomically precise structure by high-
and thermal activation at 250 °C, followed by planarization and resolution STM (Fig. 25a and d).267 STS analysis revealed the
graphitization at 440 °C into atomically precise GNR 123 with electronic bandgap of N = 13 GNR 140 on Au(111) to be
the length of up to approximately 100 nm,260 which could be approximately 1.4 eV, which was approximately 1 eV smaller
revealed by in situ high-resolution STM analysis. than the STS bandgap of N = 7 GNR 136.261, 263
By using 10,10′-dibromo-9,9′-bianthryl (134) as the In 2015, these authors reported a GNR heterojunction or
monomer instead of monomer 121, we could obtain N = 7 block copolymer, consisting of two GNR segments with
different widths.39 Through co-sublimation of monomers 134

18 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 19 of 28 Chemical Society Reviews
Journal Name ARTICLE

and 138, a mixture of N = 7–13 GNR heterojunctions such as which enabled the selective synthesis of the desired N = 5
141 could be obtained, as revealed by in situ STM observation armchair GNR structure.
(Fig. 26). STM and STS investigations revealed that the N = 7– Moreover, with Ruffieux and Fasel we developed a synthetic
13 GNR heterojunctions have height-dependent electronic route toward cove-edged GNR 146 employing 11,11′-dibromo-
structures, which are similar to that of type I semiconductor 5,5′-bischrysene (144) as the monomer (Fig. 27a and c).108
junctions, thereby demonstrating molecular bandgap Whereas a variety of GNRs with armchair-type edges have
engineering in a single strand of GNR. been achieved, GNR 146 is the first GNR with the cove edge
In the same year, with Fuchs and Chi we described a surface structure. Short dimer and tetramer of GNR 146 were
synthesis of N = 5 armchair GNRs on Au(111), starting from separately synthesized in solution as model compounds, and
1,4,5,8-tetrabromonaphthalene (142) as the monomer (Fig. 27a single-crystal X-ray analysis of the tetramer revealed non-
and b).268 In contrast to above-mentioned examples, the planar structures of such cove-edged GNRs with alternate “up-
preparation of GNR 142 did not require the final down” conformations of the peripheral benzene rings. DFT
cyclodehydrogenation step and could be completed at calculations predicted a bandgap of 1.70 eV for cove-edged
significantly lower temperature, i.e., ~300 °C. High-resolution GNR 146, which is relatively lower than that of slightly broader
STM analyses demonstrated that Au-naphthalene hybrid, GNR 129.253
bis(1,8-naphthylene)diaurate, was formed as an intermediate,

Fig. 25 (a) Surface-assisted synthesis of N = 7 armchair GNR 136, chiral (3,1)-GNR 137, and N = 13 armchair GNR 140. (b)–(d)
STM images of (b) GNR 136 on an Au(111) surface, (c) GNR 137 on a Cu(111) surface, and (d) GNR 140 on an Au(111) surface
with (b),(d) partly or (c) completely overlaid molecular models (light blue). Panel b also shows partially overlaid DFT-based STM
simulation (gray scale). The circular features in panel c are bromine atoms trapped between GNRs. (b) Reprinted by permission
from Macmillan Publishers Ltd: Nature (Ref. 37), Copyright (2010). (c),(d) Reprinted with permission from (c) Ref. 266; Copyright
2014 and (d) Ref. 267; Copyright 2013, American Chemical Society.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 19
 Chemical Society Reviews Page 20 of 28
ARTICLE Journal Name

(a) (b)

N = 7–13 GNR heterojunction 141

Fig. 26 (a) Chemical structure of N = 7–13 GNR heterojunction 141 and (b) its high-resolution STM image on an Au(111)
surface. Inset: STM image of a larger area, showing various N = 7–13 GNR heterojunctions. Reprinted by permission from
Macmillan Publishers Ltd: Nature Nanotechnology (Ref. 39), Copyright (2015).

Fig. 27 (a) Surface-assisted synthesis of N = 5 armchair GNR 143 and cove-edged GNR 146. (b),(c) STM images on Au(111)
surfaces of (b) GNR 143 and (c) GNR 146.108 (b) Inset: DFT-simulated STM image of GNR 143. Reprinted with permission from
Ref. 268; Copyright 2015, American Chemical Society.

Whereas most of the surface fabrication of GNRs has thus GNR 149 from this monomer. In 2015, Basagni and Sedona et
far been performed with triphenylene- and bianthryl-based al. reported the synthesis of N = 6 armchair GNR 152 from
monomers 121 and 134, respectively, and their derivatives, it is dibromo-p-terphenyl 150 through the formation of poly(para-
also possible to design feasible syntheses based on simpler phenylene) (PPP 151) and subsequent fusion of neighbouring
oligophenylene monomers. In 2014, Amsharov et al. reported PPPs (Fig. 28a).270 By controlling the annealing temperature,
an attempt to synthesize N = 15 armchair GNR 149 from PPP 151 and GNR 152 could be obtained with high selectivity
dibromo-p-pentaphenyl 147 as the monomer (Fig. 28a).269 STM and their atomically precise structures were revealed by STM
analysis revealed the formation of broad GNRs with a width of observations (Fig. 28e and f, respectively). Additionally, Endo
2.1 nm, consistent with the molecular models (Fig. 28c and d). et al. showed that GNRs can be prepared on a Au(111) surface
However, a certain amount of defects could not be avoided, from n-alkane as the monomer, but precise structural control
suggesting difficulties in fabricating atomically precise N = 15 remains elusive.271

20 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 21 of 28 Chemical Society Reviews
Journal Name ARTICLE

Fig. 28 Surface-assisted syntheses of (a) N = 15 armchair GNR 149 from dibromo-p-pentaphenyl 147 and (b) N = 6 armchair
GNR 152 from dibromo-p-terphenyl 150. (c)–(f) STM images of (c),(d) GNR 149, (e) PPP 151 and (f) GNR 152 on Au(111)
surfaces with partly overlaid molecular models. (c),(d) Reprinted from Ref. 269, Copyright (2014), with permission from Elsevier.
(e),(f) Reprinted with permission from Ref. 270; Copyright 2015, American Chemical Society.

N-doping of GNRs under UHV conditions. Similar to the monomers 156 and 121, respectively (Fig. 29a).38 In an STM
solution-mediated synthesis, selectively N-doped GNRs can be image of GNR heterojunction 157, the N-doped GNR segment
fabricated on metal surfaces under UHV conditions by using N- cannot be distinguished from the non-doped segment at first
doped monomers.38, 272, 273 For example, Bronner, Hecht and glance, but the attractive antiparallel alignment between the N-
Tegeder et al. reported that the use of 4,4′-(6,11-dibromo-1,4- doped segments provides an indication (Fig. 29c). Moreover,
diphenyltriphenylene-2,3-diyl)dipyridine (153) as the monomer the differential conductance dI/dV maps exhibited a clear
led to the formation of N-doped GNR 155 on a Au(111) inversion of the contrast when measured at bias voltages of –
surface, following the procedure developed for the preparation 0.35 and –1.65 V (Fig. 29e and f, respectively), which enabled
of non-doped GNRs (Fig. 29a).272 With Du and Gao we assignment of the N-doped and non-doped segments as
revealed atomically precise structures of N-doped GNR 155 by highlighted in blue and light grey, respectively, in Fig. 29d.
high-resolution STM, showing an interesting side-by-side GNR heterojunction 157 featured a type II staggered gap
alignment with the neighbouring GNRs in an antiparallel configuration with a band offset of ~0.5 eV, thus realizing a
arrangement, which was slightly shifted to maximize the molecular p-n junction in a single GNR.
attractive N···H interactions (Fig. 29b).273 Such alignment was Although the surface-assisted synthesis enabled the
not observed for non-doped chevron-type GNR 123, which preparation and characterization of atomically precise GNRs
showed apparently no interaction between two GNRs.37, 38 with different widths, edge structures, heteroatom doping and
Moreover, chevron-type GNRs with different degree of N- heterojunctions, such GNRs are all bound to the metal surfaces
doping could be synthesized, containing one, two or four and thus cannot be directly integrated into electronic devices.
nitrogen atoms in each repeating unit, by employing This makes it imperative to develop a reliable method for
tetraphenyltriphenylene-based monomers with different degrees cleanly transferring the GNRs from the metal surfaces onto
of N-doping, such as 153 and 5,5′-(6,11-dibromo-1,4- Si/SiO2 or other dielectric substrates. One way to achieve this is
diphenyltriphenylene-2,3-diyl)dipyrimidine (156) (Fig. 29).38, to grow the GNRs on epitaxial Au(111) films on mica
272, 273
Theoretical as well as experimental investigations substrates. Both the mica substrates and the thin gold films can
showed that the N-doping drastically lowered the electronic be easily removed from the GNRs, allowing their transfer onto
energy levels of the GNRs to induce n-type semiconductor an arbitrary substrate, such as SiO2, CaF2, and Al2O3.38 This
properties, while not significantly affecting the bandgap. The transfer method allowed the fabrication of working FET
shift of the energy levels critically depends on the degree of N- devices based on surface-synthesized GNRs.274 Nevertheless,
doping, which enabled precise tuning of the energy offset by further improvements in the transfer and device fabrication
molecularly controlling the degree of the doping. processes are needed to obtain GNR-based FET devices with
In 2014, together with Fasel and co-workers, we reported the the high performance predicted by theoretical studies. On the
synthesis of GNR heterojunction 157, consisting of short other hand, the direct growth of GNRs on insulating substrates
segments of N-doped and non-doped chevron-type GNRs, is more desirable because it will allow for the fabrication of
through the alternating deposition of N- and non-doped electronic devices without the complicated transfer process.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 21
 Chemical Society Reviews Page 22 of 28
ARTICLE Journal Name

One possible way to achieve this goal is to use photo-induced could indeed be converted to GNR-like structures on a mica
coupling of dibrominated monomers followed by graphitization substrate, although obtaining precise structural control is still in
under e-bean irradiation.275 Using this method, monomer 134 progress.

Fig. 29 (a) Surface-assisted synthesis of N-doped chevron-type GNR 155 and GNR heterojunction 157. (b) High-resolution STM
image of N-doped GNR 155, showing an antiparallel alignment to maximize the attractive N···H interactions. DFT-based STM
simulation model and a formula chemical structure are partially overlaid. Reprinted with permission from Ref. 273; Copyright
2014, AIP Publishing LLC. (c),(d) STM images of GNR heterojunction 157. In panel d, the N-doped and non-doped GNR
segments are highlighted in blue and light grey, respectively, as determined from the panels e and f. (e),(f) Differential
conductance dI/dV maps observed at bias voltages of (e) –0.35 V and (f) –1.65 V. The heterostructure profiles seen in the panel c
are drawn as blue or white dashed lines in panels d–f as a guide to the eye. Scale bars in panels (c)–(f) indicates 2 nm. Adapted by
permission from Macmillan Publishers Ltd: Nature Nanotechnology (Ref. 38), Copyright (2014).

Synthesis under CVD conditions. The surface-assisted GNR employed as monomers to obtain bulk films of multilayer
synthesis can reliably produce atomically precise structures, but GNRs with three different widths, corresponding to N = 7, 5
this method under UHV conditions requires complex and and 9 armchair GNRs, respectively.
expensive setups and is highly time-consuming, which hinders The GNR films CVD-grown on Au(111) surfaces could be
the preparation of large amounts of GNRs and thus their transferred onto any substrate using a wet process, which
practical application. Therefore, it is straightforward to attempt enabled UV–Vis absorption analysis of the GNRs. The
to synthesize GNRs under low-vacuum conditions with simpler absorption spectra revealed optical bandgaps of 0.8, 1.6 and 1.3
setups. In 2014, Sakaguchi and Nakae et al. reported the eV for N = 5, 7 and 9 GNRs, respectively, which was in
fabrication of GNR films under CVD conditions at a pressure agreement with the theoretically predicted trend. FET devices
of 1 Torr with a flow of argon gas.276 The synthesis was were also fabricated on transferred GNR films, exhibiting a
performed by annealing dihalogenated monomers on Au(111) charge-carrier mobility of up to 10–4 cm2/V·s. Moreover, the
surfaces, similar to the UHV method. Monomer 134, a mixture GNR films also showed photoconductivity with a current gain
of 3,9-dibromoperylene and 3,10-dibromoperylene, and 1,4- upon illumination of up to 7.3%, which is better than the value
bis(4-bromophenyl)-2,3,6,11-tetraphenyltriphenylene were of 2.7% measured for P3HT. This result indicated that such

22 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 23 of 28 Chemical Society Reviews
Journal Name ARTICLE

CVD-grown GNRs could function as excellent in SWCNTs.278, 279 The GNRs fabricated inside the SWCNTs
photoconductors. Nevertheless, more detailed studies and feature highly uniform widths and very smooth edge structures
comprehensive characterizations are necessary to elucidate if compared to top-down fabricated GNRs, but the structural
the CVD-grown GNRs are chemically identical as GNRs precision achievable by this method is considerably lower than
fabricated from the same monomers under the UHV conditions. that of the other bottom-up synthetic approaches described in
the previous section. Moreover, selective removal of the CNTs
Synthesis of GNRs confined in carbon nanotubes without affecting the confined GNRs is highly challenging,
hindering further studies and application of such GNRs.
Bottom-up GNR synthesis has also been reported through
thermal or electron (e)-beam mediated polymerization and
fusion of aromatic molecules that are confined inside single-
walled CNTs (SWCNTs).277-279 In 2011, Talyzin and Anoshkin
IV. Conclusions and outlook
et al. demonstrated that perylene and coronene confined in Recent advancements in the chemical synthesis of
SWCNTs could be converted into GNRs encapsulated in the nanographenes with newly developed “non-conventional”
SWCNTs (GNR@SWCNT) by heating at approximately 400– methods have vastly expanded the scope of available graphene
500 °C (Fig. 30a).277 The aromatic molecules were closely molecules, including a variety of symmetries, configurations,
aligned one-dimensionally inside the SWCNT, enabling the embedded seven- or eight-membered rings, heteroatom doping,
polymerization and fusion into GNRs. The structures of the and edge functionalization. The synthesis was further extended
resulting GNRs were dependent on the starting monomer. In to the longitudinally extended polymeric systems, providing
2015, Shinohara et al. succeeded in studying the optical access to structurally well-defined GNRs with varying
properties of the GNRs inside SWCNTs by covalent configurations, i.e., different widths, lengths, edge structures
functionalization of the nanotube walls with 4- and selectively doped heteroatoms. Precise GNR synthesis has
bromobenzenediazonium tetrafluoroborate.280 The excitonic been achieved using both the conventional solution-mediated
absorption peaks of the nanotubes were efficiently suppressed, method and the modern surface-based approach under UHV
revealing the optical transitions of the coronene-based GNRs at conditions. The structural variations in graphene molecules and
1.5 and 3.4 eV. GNRs have allowed fine-tuning of their (opto-)electronic
properties, which would be the basis for the future application
of such nanocarbon materials.
In particular, heteroatom doping was found to be an
effective strategy modulating the electronic properties of
graphene molecules and GNRs. Heteroatom doping in different
structures with varying doping positions and concentrations, as
well as the incorporation of other main group elements beyond
Fig. 30 (a) A TEM image of a GNR@SWCNT prepared from the examples summarized above, would further enrich their
coronene (top) and its model (bottom); light blue: GNR, red: chemistry. Particularly, further developments of B-, BN- and P-
SWCNT. Reprinted with permission from Ref. 277; Copyright doped graphene molecules, as well as syntheses of silicon (Si)-,
2011, American Chemical Society. (b) A schematic illustration germanium (Ge)- and selenium (Se)-doped graphene molecules
of the confinement of fullerene derivative 158 in a SWCNT; are awaited. Regarding GNRs, the fabrication of N-doped
grey: carbon, red: oxygen, purple: nitrogen, yellow: sulphur. (c) structures with different configurations and doping
An aberration-corrected high-resolution TEM image, (d) a
concentrations and the preparation of S-, B-, or BN-doped
simulated TEM image, and (e) a molecular model of a GNR
with sulphur-terminated edges confined in a SWCNT; grey: analogues will be an important next step. Pushing the limit of
carbon, yellow: sulphur. (b), (d), (e), (f) Adapted by permission the size and doping concentration will not only provide new
from Macmillan Publishers Ltd: Nature Materials (Ref. 278), materials with interesting properties but also enable elucidation
Copyright (2011). of the fundamental structure-property relationships of
heteroatom-doped graphene molecules and GNRs.
In 2011, Khlobystov et al. reported the fabrication of Although most of the GNRs synthesized to date feature, in
GNR@SWCNT with sulphur-terminated edges from S- principle, armchair edge structures, GNRs with a zigzag edge
containing fullerene derivative 158 (Fig. 30b) or a mixture of configuration are predicted to show localized edge states that
pristine fullerene and tetrathiafulvalene (TTF) confined in can be spin polarized, and thus these GNRs are interesting for
SWCNTs.278 By e-beam irradiation, such monomers could be spintronic applications.27-29 We have been working on the
fused to S-doped GNRs inside a SWCNT, where the S atoms surface-assisted synthesis of partial and full zigzag GNRs and
terminated the reactive edges of the as-formed GNRs (Fig. 30c- have obtained positive indications that such GNRs indeed
e). This is in contrast to the fact that pristine fullerenes are possess localized states at the edges.
transformed into narrower guest-SWCNTs inside host- In addition to heteroatom doping and the zigzag edge
SWCNTs through a similar treatment.281 Additionally, such S- configuration, further major challenges in the synthesis of
doped GNRs could also be generated from TTF alone confined GNRs include 1) obtaining GNRs with different widths,

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 23
 Chemical Society Reviews Page 24 of 28
ARTICLE Journal Name

particularly lateral extension over 3 nm to achieve a bandgap 19. K. K. Baldridge and J. S. Siegel, Angew. Chem. Int. Ed., 2013, 52,
5436.
smaller than 1 eV; 2) incorporating non-six-membered rings, 20. M. Ball, Y. Zhong, Y. Wu, C. Schenck, F. Ng, M. Steigerwald, S.
such as five-, seven- or eight-membered rings, which will also Xiao and C. Nuckolls, Acc. Chem. Res., 2015, 48, 267.
serve as models of grain boundaries in graphene; 3) structurally 21. W. Pisula, X. L. Feng and K. Müllen, Chem. Mater., 2011, 23,
554.
distorting GNRs in similar manners to contorted graphene
22. Y. Morita, S. Suzuki, K. Sato and T. Takui, Nature Chem., 2011,
molecules; 4) achieving greater control in fabricating GNR 3, 197.
heterojunctions or block copolymers to form longer “blocks” 23. Z. Sun, Z. Zeng and J. Wu, Chem. Asian J., 2013, 8, 2894.
and 5) functionalizing the GNR edges and/or terminals, for 24. X. Li, X. Wang, L. Zhang, S. Lee and H. Dai, Science, 2008, 319,
1229.
example, to tune the energy levels with electron-donating/- 25. A. Narita, X. Feng and K. Müllen, Chem. Rec., 2015, 15, 295.
withdrawing groups or to enhance the affinity to desired 26. O. V. Yazyev, Acc. Chem. Res., 2013, 46, 2319.
substrates or electrode materials. These are all important 27. M. Terrones, A. R. Botello-Méndez, J. Campos-Delgado, F.
López-Urías, Y. I. Vega-Cantú, F. J. Rodríguez-Macías, A. L.
challenges for the future nanoelectronic and optoelectronic Elías, E. Muñoz-Sandoval, A. G. Cano-Márquez, J.-C. Charlier
applications of such nanographene materials. and H. Terrones, Nano Today, 2010, 5, 351.
28. Y. W. Son, M. L. Cohen and S. G. Louie, Nature, 2006, 444, 347.
Acknowledgements 29. O. V. Yazyev, Rep. Prog. Phys., 2010, 73, 056501.
30. W. Y. Kim and K. S. Kim, Nature Nanotech., 2008, 3, 408.
We acknowledge all of our distinguished partner groups and 31. X.-R. Wang, Y. Shi and R. Zhang, Chin. Phys. B, 2013, 22,
dedicated associates, who enabled our contributions to the 098505.
achievements described in this article. We thank the financial 32. M. Han, B. Özyilmaz, Y. Zhang and P. Kim, Phys. Rev. Lett.,
2007, 98, 206805.
support by EU Projects GENIUS (ITN-264694), UPGRADE 33. Z. Chen, Y. Lin, M. Rooks and P. Avouris, Physica E, 2007, 40,
and MoQuaS, ERC-Adv.-Grant 267160 (NANOGRAPH), 228.
Graphene Flagship (No. CNECT-ICT-604391), the Office of 34. L. Tapaszto, G. Dobrik, P. Lambin and L. P. Biro, Nature
Nanotech., 2008, 3, 397.
Naval Research BRC Program (molecular synthesis and 35. D. V. Kosynkin, A. L. Higginbotham, A. Sinitskii, J. R. Lomeda,
characterization) and DFG Priority Program SPP 1459. We are A. Dimiev, B. K. Price and J. M. Tour, Nature, 2009, 458, 872.
also thankful to fruitful collaborations with BASF SE, 36. L. Jiao, L. Zhang, X. Wang, G. Diankov and H. Dai, Nature,
2009, 458, 877.
Ludwigshafen.
37. J. Cai, P. Ruffieux, R. Jaafar, M. Bieri, T. Braun, S. Blankenburg,
M. Muoth, A. P. Seitsonen, M. Saleh, X. Feng, K. Müllen and R.
Notes and references Fasel, Nature, 2010, 466, 470.
a
Max Planck Institute for Polymer Research 38. J. Cai, C. A. Pignedoli, L. Talirz, P. Ruffieux, H. Söde, L. Liang,
V. Meunier, R. Berger, R. Li, X. Feng, K. Müllen and R. Fasel,
Ackermannweg 10, 55128 Mainz, Germany. E-mail: muellen@mpip- Nature Nanotech., 2014, 9, 896.
mainz.mpg.de 39. Y.-C. Chen, T. Cao, C. Chen, Z. Pedramrazi, D. Haberer, D. G. de
b
Center for Advancing Electronics Dresden (cfaed) & Department of Oteyza, F. R. Fischer, S. G. Louie and M. F. Crommie, Nature
Nanotech., 2015, 10, 156.
Chemistry and Food Chemistry, Dresden University of Technology 40. M. D. Watson, A. Fechtenkötter and K. Müllen, Chem. Rev.,
Walther-Hempel-Bau Mommsenstrasse 4, 01062 Dresden, Germany 2001, 101, 1267.
41. W. Jiang, Y. Li and Z. Wang, Chem. Soc. Rev., 2013, 42, 6113.
1. K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, 42. B. Schmaltz, T. Weil and K. Müllen, Adv. Mater., 2009, 21, 1067.
S. V. Dubonos, I. V. Grigorieva and A. A. Firsov, Science, 2004, 43. Y. Segawa, T. Maekawa and K. Itami, Angew. Chem. Int. Ed.,
306, 666. 2015, 54, 66.
2. A. K. Geim and K. S. Novoselov, Nat Mater, 2007, 6, 183. 44. A. Sygula, Eur. J. Org. Chem., 2011, 2011, 1611.
3. R. F. Service, Science, 2009, 324, 875. 45. D. Wu, H. Ge, S. H. Liu and J. Yin, RSC Adv., 2013, 3, 22727.
4. K. S. Novoselov, V. I. Falko, L. Colombo, P. R. Gellert, M. G. 46. Z. Sun, Q. Ye, C. Chi and J. Wu, Chem. Soc. Rev., 2012, 41,
Schwab and K. Kim, Nature, 2012, 490, 192. 7857.
5. F. Schwierz, Nature Nanotech., 2010, 5, 487. 47. Y. Tobe, Chem. Rec., 2015, 15, 86.
6. R. Rieger and K. Müllen, J. Phys. Org. Chem., 2010, 23, 315. 48. V. M. Tsefrikas and L. T. Scott, Chem. Rev., 2006, 106, 4868.
7. M. Bacon, S. J. Bradley and T. Nann, Part. Part. Syst. Charact., 49. Z. Sun, Z. Zeng and J. Wu, Acc. Chem. Res., 2014, 47, 2582.
2014, 31, 415. 50. Z. Sun and J. Wu, J. Mater. Chem., 2012, 22, 4151.
8. S. Kim, S. W. Hwang, M.-K. Kim, D. Y. Shin, D. H. Shin, C. O. 51. T. Kubo, Chem. Lett., 2015, 44, 111.
Kim, S. B. Yang, J. H. Park, E. Hwang, S.-H. Choi, G. Ko, S. 52. T. Kubo, Chem. Rec., 2015, 15, 218.
Sim, C. Sone, H. J. Choi, S. Bae and B. H. Hong, ACS Nano, 53. A. Konishi, Y. Hirao, H. Kurata, T. Kubo, M. Nakano and K.
2012, 6, 8203. Kamada, Pure and Applied Chemistry, 2014, 86, 497.
9. J. Wu, W. Pisula and K. Müllen, Chem. Rev., 2007, 107, 718. 54. T. Amaya and T. Hirao, Chem. Rec., 2015, 15, 310.
10. K. Müllen, ACS Nano, 2014, 8, 6531. 55. M. Mojica, J. A. Alonso and F. Méndez, J. Phys. Org. Chem.,
11. R. Scholl and C. Seer, Liebigs Ann. Chem., 1912, 394, 111. 2013, 26, 526.
12. R. Scholl and C. Seer, Chem. Ber., 1922, 55, 330. 56. T. Jin, J. Zhao, N. Asao and Y. Yamamoto, Chem.—Eur. J., 2014,
13. R. Scholl, C. Seer and R. Weitzenböck, Chem. Ber., 1910, 43, 20, 3554.
2202. 57. B. M. Schmidt and D. Lentz, Chem. Lett., 2014, 43, 171.
14. E. Clar and J. F. Stephen, Tetrahedron, 1965, 21, 467. 58. H. F. Bettinger and C. Tönshoff, Chem. Rec., 2015, 15, 364.
15. E. Clar and W. schmidt, Tetrahedron, 1979, 35, 2673. 59. M. Watanabe, K.-Y. Chen, Y. J. Chang and T. J. Chow, Acc.
16. E. Clar and D. G. Stewart, J Am Chem Soc, 1953, 75, 2667. Chem. Res., 2013, 46, 1606.
17. L. Chen, Y. Hernandez, X. Feng and K. Müllen, Angew. Chem. 60. A. Mateo-Alonso, Chem. Soc. Rev., 2014, 43, 6311.
Int. Ed., 2012, 51, 7640. 61. U. H. F. Bunz, J. U. Engelhart, B. D. Lindner and M. Schaffroth,
18. X. Yan and L.-s. Li, J. Mater. Chem., 2011, 21, 3295. Angew. Chem. Int. Ed., 2013, 52, 3810.
62. L. Chen, C. Li and K. Müllen, J. Mater. Chem. C, 2014, 2, 1938.
63. W. Jiang, Y. Li and Z. Wang, Acc. Chem. Res., 2014, 47, 3135.

24 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 25 of 28 Chemical Society Reviews
Journal Name ARTICLE

64. N. Saleh, C. Shen and J. Crassous, Chem. Sci., 2014, 5, 3680. 101. M. Shimizu and T. Hiyama, Eur. J. Org. Chem., 2013, 2013,
65. M. Gingras, Chem. Soc. Rev., 2013, 42, 968. 8069.
66. M. Gingras, G. Felix and R. Peresutti, Chem. Soc. Rev., 2013, 42, 102. C.-N. Feng, Y.-C. Hsieh and Y.-T. Wu, Chem. Rec., 2015, 15,
1007. 266.
67. M. Gingras, Chem. Soc. Rev., 2013, 42, 1051. 103. D. M. Hitt and J. M. O’Connor, Chem. Rev., 2011, 111, 7904.
68. Y. Shen and C.-F. Chen, Chem. Rev., 2012, 112, 1463. 104. K. Y. Amsharov, M. A. Kabdulov and M. Jansen, Angew. Chem.
69. K. Shi, J.-Y. Wang and J. Pei, Chem. Rec., 2015, 15, 52. Int. Ed., 2012, 51, 4594.
70. H. Zhang, D. Wu, S. Hua Liu and J. Yin, Curr. Org. Chem., 2012, 105. K. Y. Amsharov and P. Merz, J Org Chem, 2012, 77, 5445.
16, 2124. 106. T.-A. Chen and R.-S. Liu, Chem.—Eur. J., 2011, 17, 8023.
71. M. Grzybowski, K. Skonieczny, H. Butenschön and D. T. Gryko, 107. T.-A. Chen and R.-S. Liu, Org. Lett., 2011, 13, 4644.
Angew. Chem. Int. Ed., 2013, 52, 9900. 108. J. Liu, B.-W. Li, Y.-Z. Tan, A. Giannakopoulos, C. Sanchez-
72. R. Dorel, C. Manzano, M. Grisolia, W.-H. Soe, C. Joachim and A. Sanchez, D. Beljonne, P. Ruffieux, R. Fasel, X. Feng and K.
M. Echavarren, Chem. Commun., 2015, 51, 6932. Müllen, J Am Chem Soc, 2015, 137, 6097.
73. A. Matsumoto, M. Suzuki, D. Kuzuhara, H. Hayashi, N. Aratani 109. Q. Yan, K. Cai, C. Zhang and D. Zhao, Org. Lett., 2012, 14, 4654.
and H. Yamada, Angew. Chem. Int. Ed., 2015, DOI: 110. C.-W. Li, C.-I. Wang, H.-Y. Liao, R. Chaudhuri and R.-S. Liu, J
10.1002/anie.201502466. Org Chem, 2007, 72, 9203.
74. C. D. Simpson, J. D. Brand, A. J. Berresheim, L. Przybilla, H. J. 111. C. Thilgen, Angew. Chem. Int. Ed., 2012, 51, 7082.
Räder and K. Müllen, Chem.—Eur. J., 2002, 8, 1424. 112. H. Ohno, Asian J. Org. Chem., 2013, 2, 18.
75. A. A. Sarhan and C. Bolm, Chem Soc Rev, 2009, 38, 2730. 113. P. Y. Huang, C. S. Ruiz-Vargas, A. M. van der Zande, W. S.
76. S. R. Waldvogel and S. Trosien, Chem. Commun., 2012, 48, 9109. Whitney, M. P. Levendorf, J. W. Kevek, S. Garg, J. S. Alden, C.
77. L. Zhai, R. Shukla and R. Rathore, Org. Lett., 2009, 11, 3474. J. Hustedt, Y. Zhu, J. Park, P. L. McEuen and D. A. Muller,
78. B. T. King, J. Kroulík, C. R. Robertson, P. Rempala, C. L. Hilton, Nature, 2011, 469, 389.
J. D. Korinek and L. M. Gortari, J Org Chem, 2007, 72, 2279. 114. K. Kim, Z. Lee, W. Regan, C. Kisielowski, M. F. Crommie and
79. F. Morgenroth, C. Kübel, M. Müller, U. M. Wiesler, A. J. A. Zettl, ACS Nano, 2011, 5, 2142.
Berresheim, M. Wagner and K. Müllen, Carbon, 1998, 36, 833. 115. S. Kurasch, J. Kotakoski, O. Lehtinen, V. Skákalová, J. Smet, C.
80. J. L. Ormsby, T. D. Black, C. L. Hilton, Bharat and B. T. King, E. Krill, A. V. Krasheninnikov and U. Kaiser, Nano Lett., 2012,
Tetrahedron, 2008, 64, 11370. 12, 3168.
81. F. Dötz, J. D. Brand, S. Ito, L. Gherghel and K. Müllen, J Am 116. J. Lahiri, Y. Lin, P. Bozkurt, I. I. Oleynik and M. Batzill, Nature
Chem Soc, 2000, 122, 7707. Nanotech., 2010, 5, 326.
82. K. Yoshimura, L. Przybilla, S. Ito, J. D. Brand, M. Wehmeir, H. J. 117. P. B. László and L. Philippe, New J. Phys., 2013, 15, 035024.
Räder and K. Müllen, Macromol. Chem. Phys., 2001, 202, 215. 118. Y.-T. Wu and J. S. Siegel, Chem. Rev., 2006, 106, 4843.
83. X. Dou, X. Yang, G. J. Bodwell, M. Wagner, V. Enkelmann and 119. K. Yamamoto and H. Matsubara, J. Synth. Org. Chem. Jpn., 1995,
K. Müllen, Org. Lett., 2007, 9, 2485. 53, 318.
84. H. Arslan, F. J. Uribe-Romo, B. J. Smith and W. R. Dichtel, 120. J. H. Dopper and H. Wynberg, Tetrahedron Lett., 1972, 13, 763.
Chem. Sci., 2013, 4, 3973. 121. T. J. Seiders and J. S. Siegel, Chem. Britain, 1995, 31, 313.
85. A. C. Whalley, K. N. Plunkett, A. A. Gorodetsky, C. L. Schenck, 122. K. Yamamoto, T. Harada, M. Nakazaki, T. Naka, Y. Kai, S.
C.-Y. Chiu, M. L. Steigerwald and C. Nuckolls, Chem. Sci., 2011, Harada and N. Kasai, J Am Chem Soc, 1983, 105, 7171.
2, 132. 123. K. Yamamoto, Y. Saitho, D. Iwaki and T. Ooka, Angew. Chem.
86. S. J. Hein, H. Arslan, I. Keresztes and W. R. Dichtel, Org. Lett., Int. Ed. Engl., 1991, 30, 1173.
2014, 16, 4416. 124. J. Luo, X. Xu, R. Mao and Q. Miao, J Am Chem Soc, 2012, 134,
87. H. Arslan, J. D. Saathoff, D. N. Bunck, P. Clancy and W. R. 13796.
Dichtel, Angew. Chem. Int. Ed., 2012, 51, 12051. 125. K. Y. Cheung, X. Xu and Q. Miao, J Am Chem Soc, 2015, 137,
88. Q. Zhang, H. Peng, G. Zhang, Q. Lu, J. Chang, Y. Dong, X. Shi 3910.
and J. Wei, J Am Chem Soc, 2014, 136, 5057. 126. A. Pradhan, P. Dechambenoit, H. Bock and F. Durola, J Org
89. A. A. Gorodetsky, C.-Y. Chiu, T. Schiros, M. Palma, M. Cox, Z. Chem, 2013, 78, 2266.
Jia, W. Sattler, I. Kymissis, M. Steigerwald and C. Nuckolls, 127. K. Kawasumi, Q. Zhang, Y. Segawa, L. T. Scott and K. Itami,
Angew. Chem. Int. Ed., 2010, 49, 7909. Nature Chem., 2013, 5, 739.
90. C.-Y. Chiu, B. Kim, A. A. Gorodetsky, W. Sattler, S. Wei, A. 128. Q. Zhang, K. Kawasumi, Y. Segawa, K. Itami and L. T. Scott, J
Sattler, M. Steigerwald and C. Nuckolls, Chem. Sci., 2011, 2, Am Chem Soc, 2012, 134, 15664.
1480. 129. K. Mochida, K. Kawasumi, Y. Segawa and K. Itami, J Am Chem
91. L. Chen, S. R. Puniredd, Y.-Z. Tan, M. Baumgarten, U. Soc, 2011, 133, 10716.
Zschieschang, V. Enkelmann, W. Pisula, X. Feng, H. Klauk and 130. R. Salcedo, L. E. Sansores, A. Picazo and L. Sansón, J. Mol.
K. Müllen, J Am Chem Soc, 2012, 134, 17869. Struct. (THEOCHEM), 2004, 678, 211.
92. L. Chen, K. S. Mali, S. R. Puniredd, M. Baumgarten, K. Parvez, 131. B. Thulin and O. Wennerström, Acta. Chem. Scand. B, 1976, 30b,
W. Pisula, S. De Feyter and K. Müllen, J Am Chem Soc, 2013, 369.
135, 13531. 132. C.-N. Feng, M.-Y. Kuo and Y.-T. Wu, Angew. Chem. Int. Ed.,
93. D. Pérez, D. Peña and E. Guitián, Eur. J. Org. Chem., 2013, 2013, 2013, 52, 7791.
5981. 133. Y. Sakamoto and T. Suzuki, J Am Chem Soc, 2013, 135, 14074.
94. D. Peña, S. Escudero, D. Pérez, E. Guitián and L. Castedo, 134. R. W. Miller, A. K. Duncan, S. T. Schneebeli, D. L. Gray and A.
Angew. Chem. Int. Ed., 1998, 37, 2659. C. Whalley, Chem.—Eur. J., 2014, 20, 3705.
95. D. Peña, D. Pérez, E. Guitián and L. Castedo, Org. Lett., 1999, 1, 135. F. Schlütter, T. Nishiuchi, V. Enkelmann and K. Müllen, Angew.
1555. Chem. Int. Ed., 2014, 53, 1538.
96. C. Romero, D. Peña, D. Pérez and E. Guitián, Chem.–Eur. J., 136. X. Wang, G. Sun, P. Routh, D.-H. Kim, W. Huang and P. Chen,
2006, 12, 5677. Chem. Soc. Rev., 2014, 43, 7067.
97. J. M. Alonso, A. E. Díaz-Álvarez, A. Criado, D. Pérez, D. Peña 137. U. N. Maiti, W. J. Lee, J. M. Lee, Y. Oh, J. Y. Kim, J. E. Kim, J.
and E. Guitián, Angew. Chem. Int. Ed., 2012, 51, 173. Shim, T. H. Han and S. O. Kim, Adv. Mater., 2014, 26, 40.
98. B. Schuler, S. Collazos, L. Gross, G. Meyer, D. Pérez, E. Guitián 138. H. T. Liu, Y. Q. Liu and D. B. Zhu, J. Mater. Chem., 2011, 21,
and D. Peña, Angew. Chem. Int. Ed., 2014, 53, 9004. 3335.
99. Z.-h. Zhou and T. Yamamoto, J. Organomet. Chem., 1991, 414, 139. X.-Y. Wang, J.-Y. Wang and J. Pei, Chem.—Eur. J., 2015, 21,
119. 3528.
100. E. C. Rüdiger, M. Porz, M. Schaffroth, F. Rominger and U. H. F. 140. P. G. Campbell, A. J. V. Marwitz and S. Y. Liu, Angew. Chem.
Bunz, Chem.—Eur. J., 2014, 20, 12725. Int. Ed., 2012, 51, 6074.
141. M. J. D. Bosdet and W. E. Piers, Can. J. Chem., 2009, 87, 8.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 25
 Chemical Society Reviews Page 26 of 28
ARTICLE Journal Name

142. M. Takase, V. Enkelmann, D. Sebastiani, M. Baumgarten and K. 175. J. S. A. Ishibashi, J. L. Marshall, A. Mazière, G. J. Lovinger, B.
Müllen, Angew. Chem. Int. Ed., 2007, 46, 5524. Li, L. N. Zakharov, A. Dargelos, A. Graciaa, A. Chrostowska and
143. M. Takase, T. Narita, W. Fujita, M. S. Asano, T. Nishinaga, H. S.-Y. Liu, J Am Chem Soc, 2014, 136, 15414.
Benten, K. Yoza and K. Müllen, J. Am. Chem. Soc., 2013, 135, 176. B. Neue, J. F. Araneda, W. E. Piers and M. Parvez, Angew. Chem.
8031. Int. Ed., 2013, 52, 9966.
144. H. Uoyama, K. Goushi, K. Shizu, H. Nomura and C. Adachi, 177. X. Wang, F. Zhang, J. Liu, R. Z. Tang, Y. B. Fu, D. Q. Wu, Q.
Nature, 2012, 492, 234. Xu, X. D. Zhuang, G. F. He and X. L. Feng, Org. Lett., 2013, 15,
145. E. Gońka, P. J. Chmielewski, T. Lis and M. Stępień, J Am Chem 5714.
Soc, 2014, 136, 16399. 178. T. Hatakeyama, S. Hashimoto, S. Seki and M. Nakamura, J Am
146. S. M. Draper, D. J. Gregg and R. Madathil, J Am Chem Soc, 2002, Chem Soc, 2011, 133, 18614.
124, 3486. 179. M. J. D. Bosdet, W. E. Piers, T. S. Sorensen and M. Parvez,
147. S. M. Draper, D. J. Gregg, E. R. Schofield, W. R. Browne, M. Angew. Chem. Int. Ed., 2007, 46, 4940.
Duati, J. G. Vos and P. Passaniti, J Am Chem Soc, 2004, 126, 180. D. J. H. Emslie, W. E. Piers and M. Parvez, Angew. Chem. Int.
8694. Ed., 2003, 42, 1252.
148. L. P. Wijesinghe, B. S. Lankage, G. M. O. Maille, S. D. Perera, D. 181. X.-Y. Wang, F.-D. Zhuang, R.-B. Wang, X.-C. Wang, X.-Y. Cao,
Nolan, L. Wang and S. M. Draper, Chem. Commun., 2014, 50, J.-Y. Wang and J. Pei, J Am Chem Soc, 2014, 136, 3764.
10637. 182. X.-Y. Wang, F.-D. Zhuang, X.-C. Wang, X.-Y. Cao, J.-Y. Wang
149. J. F. Wei, B. Han, Q. A. Guo, X. Y. Shi, W. L. Wang and N. Wei, and J. Pei, Chem. Commun., 2015, DOI: DOI:
Angew. Chem. Int. Ed., 2010, 49, 8209. 10.1039/C4CC10105G.
150. B. He, A. B. Pun, L. M. Klivansky, A. M. McGough, Y. Ye, J. 183. G. Li, W.-W. Xiong, P.-Y. Gu, J. Cao, J. Zhu, R. Ganguly, Y. Li,
Zhu, J. Guo, S. J. Teat and Y. Liu, Chem. Mater., 2014, 26, 3920. A. C. Grimsdale and Q. Zhang, Org. Lett., 2015, 17, 560.
151. R. Berger, A. Giannakopoulos, P. Ravat, M. Wagner, D. 184. D. Wu, H. Zhang, J. Liang, H. Ge, C. Chi, J. Wu, S. H. Liu and J.
Beljonne, X. Feng and K. Müllen, Angew. Chem. Int. Ed., 2014, Yin, J Org Chem, 2012, 77, 11319.
53, 10520. 185. M. Krieg, F. Reicherter, P. Haiss, M. Ströbele, K. Eichele, M.-J.
152. R. Berger, M. Wagner, X. Feng and K. Müllen, Chem. Sci., 2015, Treanor, R. Schaub and H. F. Bettinger, Angew. Chem. Int. Ed.,
6, 436. 2015, DOI: 10.1002/anie.201412165.
153. S. Ito, Y. Tokimaru and K. Nozaki, Chem. Commun., 2015, 51, 186. Y. Matano and H. Imahori, Org. Biomol. Chem., 2009, 7, 1258.
221. 187. T. Baumgartner and R. Réau, Chem. Rev., 2006, 106, 4681.
154. S. Ito, Y. Tokimaru and K. Nozaki, Angew. Chem. Int. Ed., 2015, 188. M. Stolar and T. Baumgartner, Chem. Asian J., 2014, 9, 1212.
54, 7256. 189. T. Hatakeyama, S. Hashimoto and M. Nakamura, Org. Lett.,
155. S. C. Gadekar, B. K. Reddy and V. G. Anand, Chem. Commun., 2011, 13, 2130.
2015, 51, 8342. 190. S. Hashimoto, S. Nakatsuka, M. Nakamura and T. Hatakeyama,
156. K. Skonieczny and D. T. Gryko, J Org Chem, 2015, 80, 5753. Angew. Chem. Int. Ed., 2014, 53, 14074.
157. M. E. Cinar and T. Ozturk, Chem. Rev., 2015, 115, 3036. 191. P.-A. Bouit, A. Escande, R. Szűcs, D. Szieberth, C. Lescop, L.
158. K. Takimiya, I. Osaka, T. Mori and M. Nakano, Acc. Chem. Res., Nyulászi, M. Hissler and R. Réau, J Am Chem Soc, 2012, 134,
2014, 47, 1493. 6524.
159. Y. Cao, X.-Y. Wang, J.-Y. Wang and J. Pei, Synlett, 2014, 25, 192. S. Sergeyev, W. Pisula and Y. H. Geerts, Chem. Soc. Rev., 2007,
313. 36, 1902.
160. K. Y. Chernichenko, V. V. Sumerin, R. V. Shpanchenko, E. S. 193. S. Ito, M. Wehmeier, J. D. Brand, C. Kübel, R. Epsch, J. P. Rabe
Balenkova and V. G. Nenajdenko, Angew. Chem. Int. Ed., 2006, and K. Müllen, Chem.–Eur. J., 2000, 6, 4327.
45, 7367. 194. L. Chen, X. Dou, W. Pisula, X. Y. Yang, D. Q. Wu, G. Floudas,
161. L. Zou, X.-Y. Wang, K. Shi, J.-Y. Wang and J. Pei, Org. Lett., X. L. Feng and K. Müllen, Chem. Commun., 2012, 48, 702.
2013, 15, 4378. 195. J. Wu, A. Fechtenkötter, J. Gauss, M. D. Watson, M. Kastler, C.
162. H. Oshima, A. Fukazawa, T. Sasamori and S. Yamaguchi, Angew. Fechtenkötter, M. Wagner and K. Müllen, J Am Chem Soc, 2004,
Chem. Int. Ed., 2015, DOI: 10.1002/anie.201501790. 126, 11311.
163. R.-Q. Lu, Y.-N. Zhou, X.-Y. Yan, K. Shi, Y.-Q. Zheng, M. Luo, 196. L. F. Dössel, V. Kamm, I. A. Howard, F. Laquai, W. Pisula, X.
X.-C. Wang, J. Pei, H. Xia, L. Zoppi, K. K. Baldridge, J. S. Siegel Feng, C. Li, M. Takase, T. Kudernac, S. De Feyter and K. Müllen,
and X.-Y. Cao, Chem. Commun., 2015, 51, 1681. J Am Chem Soc, 2012, 134, 5876.
164. X. Feng, J. Wu, M. Ai, W. Pisula, L. Zhi, J. P. Rabe and K. 197. P. Ravat, T. Marszalek, W. Pisula, K. Müllen and M. Baumgarten,
Müllen, Angew. Chem. Int. Ed., 2007, 46, 3033. J Am Chem Soc, 2014, 136, 12860.
165. C. J. Martin, B. Gil, S. D. Perera and S. M. Draper, Chem. 198. Y.-Z. Tan, B. Yang, K. Parvez, A. Narita, S. Osella, D. Beljonne,
Commun., 2011, 47, 3616. X. Feng and K. Müllen, Nat. Commun., 2013, 4, 2646.
166. S. J. Kang, J. B. Kim, C.-Y. Chiu, S. Ahn, T. Schiros, S. S. Lee, 199. C. L. Hilton, J. M. Crowfoot, P. Rempala and B. T. King, J Am
K. G. Yager, M. F. Toney, Y.-L. Loo and C. Nuckolls, Angew. Chem Soc, 2008, 130, 13392.
Chem. Int. Ed., 2012, 51, 8594. 200. Y.-Z. Tan, S. Osella, Y. Liu, B. Yang, D. Beljonne, X. Feng and
167. A. Escande and M. J. Ingleson, Chem. Commun., 2015, 51, 6257. K. Müllen, Angew. Chem. Int. Ed., 2015, DOI:
168. Z. Zhou, A. Wakamiya, T. Kushida and S. Yamaguchi, J Am 10.1002/anie.201409932.
Chem Soc, 2012, 134, 4529. 201. I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy and J.
169. S. Saito, K. Matsuo and S. Yamaguchi, J Am Chem Soc, 2012, F. Hartwig, Chem. Rev., 2009, 110, 890.
134, 9130. 202. R. Yamaguchi, S. Hiroto and H. Shinokubo, Org. Lett., 2012, 14,
170. C. Dou, S. Saito, K. Matsuo, I. Hisaki and S. Yamaguchi, Angew. 2472.
Chem. Int. Ed., 2012, 51, 12206. 203. H. Shinokubo, Proc. Jpn. Acad. Ser. B Phys. Biol. Sci., 2014, 90,
171. K. Matsuo, S. Saito and S. Yamaguchi, J Am Chem Soc, 2014, 1.
136, 12580. 204. R. Yamaguchi, S. Ito, B. S. Lee, S. Hiroto, D. Kim and H.
172. V. M. Hertz, M. Bolte, H.-W. Lerner and M. Wagner, Angew. Shinokubo, Chem. Asian J., 2013, 8, 178.
Chem. Int. Ed., 2015, DOI: 10.1002/anie.201502977. 205. K. Takagi and Y. Sakakibara, Chem. Lett., 1989, 18, 1957.
173. X.-Y. Wang, H.-R. Lin, T. Lei, D.-C. Yang, F.-D. Zhuang, J.-Y. 206. K. Ozaki, K. Kawasumi, M. Shibata, H. Ito and K. Itami, Nat.
Wang, S.-C. Yuan and J. Pei, Angew. Chem. Int. Ed., 2013, 52, Commun., 2015, 6, 6251.
3117. 207. M. N. Eliseeva and L. T. Scott, J Am Chem Soc, 2012, 134,
174. X.-Y. Wang, F.-D. Zhuang, X. Zhou, D.-C. Yang, J.-Y. Wang and 15169.
J. Pei, J. Mater. Chem. C, 2014, 2, 8152. 208. E. H. Fort, P. M. Donovan and L. T. Scott, J Am Chem Soc, 2009,
131, 16006.
209. E. H. Fort and L. T. Scott, Angew. Chem. Int. Ed., 2010, 49, 6626.

26 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012
Page 27 of 28 Chemical Society Reviews
Journal Name ARTICLE

210. E. H. Fort and L. T. Scott, Tetrahedron Lett., 2011, 52, 2051. 245. U. Kumar and T. X. Neenan, Macromolecules, 1995, 28, 124.
211. J. Li, C. Jiao, K.-W. Huang and J. Wu, Chem.—Eur. J., 2011, 17, 246. C. H. Fujimoto, M. A. Hickner, C. J. Cornelius and D. A. Loy,
14672. Macromolecules, 2005, 38, 5010.
212. E. H. Fort, M. S. Jeffreys and L. T. Scott, Chem. Commun., 2012, 247. C. E. P. Villegas, P. B. Mendonça and A. R. Rocha, Sci. Rep.,
48, 8102. 2014, 4, 6579.
213. A. Konishi, Y. Hirao, K. Matsumoto, H. Kurata and T. Kubo, 248. S. A. Jensen, R. Ulbricht, A. Narita, X. Feng, K. Müllen, T.
Chem. Lett., 2013, 42, 592. Hertel, D. Turchinovich and M. Bonn, Nano Lett., 2013, 13, 5925.
214. J. K. Stille, G. K. Noren and L. Green, J. Polym. Sci. A-1, Polym. 249. A. N. Abbas, G. Liu, A. Narita, M. Orosco, X. Feng, K. Müllen
Chem., 1970, 8, 2245. and C. Zhou, J Am Chem Soc, 2014, 136, 7555.
215. A. D. Schlüter, M. Löffler and V. Enkelmann, Nature, 1994, 368, 250. R. Konnerth, C. Cervetti, A. Narita, X. Feng, K. Müllen, A.
831. Hoyer, M. Burghard, K. Kern, M. Dressel and L. Bogani,
216. M. Löffler, A.-D. Schlüter, K. Gessler, W. Saenger, J.-M. Nanoscale, 2015, DOI: 10.1039/C4NR07378A.
Toussaint and J.-L. Brédas, Angew. Chem. Int. Ed. Engl., 1994, 251. U. Zschieschang, H. Klauk, I. B. Müller, A. J. Strudwick, T.
33, 2209. Hintermann, M. G. Schwab, A. Narita, X. Feng, K. Müllen and R.
217. K. Chmil and U. Scherf, Makromol. Chem., Rapid Commun., T. Weitz, Adv. Electron. Mater., 2015, 1, 1400010.
1993, 14, 217. 252. A. Narita, I. A. Verzhbitskiy, W. Frederickx, K. S. Mali, S. A.
218. K. Chmil and U. Scherf, Acta Polym., 1997, 48, 208. Jensen, M. R. Hansen, M. Bonn, S. De Feyter, C. Casiraghi, X.
219. U. Scherf, J. Mater. Chem., 1999, 9, 1853. Feng and K. Müllen, ACS Nano, 2014, 8, 11622.
220. M. B. Goldfinger and T. M. Swager, J Am Chem Soc, 1994, 116, 253. S. Osella, A. Narita, M. G. Schwab, Y. Hernandez, X. Feng, K.
7895. Müllen and D. Beljonne, ACS Nano, 2012, 6, 5539.
221. Z. B. Shifrina, M. S. Averina, A. L. Rusanov, M. Wagner and K. 254. L. Lafferentz, F. Ample, H. Yu, S. Hecht, C. Joachim and L. Grill,
Müllen, Macromolecules, 2000, 33, 3525. Science, 2009, 323, 1193.
222. J. S. Wu, L. Gherghel, M. D. Watson, J. X. Li, Z. H. Wang, C. D. 255. L. Grill, M. Dyer, L. Lafferentz, M. Persson, M. V. Peters and S.
Simpson, U. Kolb and K. Müllen, Macromolecules, 2003, 36, Hecht, Nature Nanotech., 2007, 2, 687.
7082. 256. M. Bieri, M. Treier, J. Cai, K. Aït-Mansour, P. Ruffieux, O.
223. T. Ikeda, N. Aratani and A. Osuka, Chem. Asian J., 2009, 4, 1248. Groning, P. Groning, M. Kastler, R. Rieger, X. Feng, K. Müllen
224. T. Tanaka and A. Osuka, Chem. Soc. Rev., 2015, 44, 943. and R. Fasel, Chem. Commun., 2009, 6919.
225. A. Tsuda and A. Osuka, Science, 2001, 293, 79. 257. L. Lafferentz, V. Eberhardt, C. Dri, C. Africh, G. Comelli, F.
226. A. Tsuda, H. Furuta and A. Osuka, Angew. Chem. Int. Ed., 2000, Esch, S. Hecht and L. Grill, Nature Chem., 2012, 4, 215.
39, 2549. 258. M. Treier, C. A. Pignedoli, T. Laino, R. Rieger, K. Müllen, D.
227. X. Y. Yang, X. Dou, A. Rouhanipour, L. J. Zhi, H. J. Rader and Passerone and R. Fasel, Nature Chem., 2011, 3, 61.
K. Müllen, J Am Chem Soc, 2008, 130, 4216. 259. M. Saleh, PhD thesis, University of Mainz (Germany), 2010.
228. L. Dössel, L. Gherghel, X. Feng and K. Müllen, Angew. Chem. 260. S. Linden, D. Zhong, A. Timmer, N. Aghdassi, J. H. Franke, H.
Int. Ed., 2011, 50, 2540. Zhang, X. Feng, K. Müllen, H. Fuchs, L. Chi and H. Zacharias,
229. A. Narita, X. Feng, Y. Hernandez, S. A. Jensen, M. Bonn, H. Phys. Rev. Lett., 2012, 108, 216801.
Yang, I. A. Verzhbitskiy, C. Casiraghi, M. R. Hansen, A. H. R. 261. P. Ruffieux, J. Cai, N. C. Plumb, L. Patthey, D. Prezzi, A. Ferretti,
Koch, G. Fytas, O. Ivasenko, B. Li, K. S. Mali, T. Balandina, S. E. Molinari, X. Feng, K. Müllen, C. A. Pignedoli and R. Fasel,
Mahesh, S. De Feyter and K. Müllen, Nature Chem., 2014, 6, 126. ACS Nano, 2012, 6, 6930.
230. K. T. Kim, J. W. Jung and W. H. Jo, Carbon, 2013, 63, 202. 262. R. Denk, M. Hohage, P. Zeppenfeld, J. Cai, C. A. Pignedoli, H.
231. K. T. Kim, J. W. Lee and W. H. Jo, Macromol. Chem. Phys., Söde, R. Fasel, X. Feng, K. Müllen, S. Wang, D. Prezzi, A.
2013, 214, 2768. Ferretti, A. Ruini, E. Molinari and P. Ruffieux, Nat. Commun.,
232. M. G. Schwab, A. Narita, S. Osella, Y. Hu, A. Maghsoumi, A. 2014, 5, 4253.
Mavrinsky, W. Pisula, C. Castiglioni, M. Tommasini, D. 263. M. Koch, F. Ample, C. Joachim and L. Grill, Nature Nanotech.,
Beljonne, X. Feng and K. Müllen, Chem. Asian J., 2015, DOI: 2012, 7, 713.
10.1002/asia.201500450. 264. J. van der Lit, M. P. Boneschanscher, D. Vanmaekelbergh, M.
233. W. H. Carothers, Trans. Faraday Soc., 1936, 32, 39. Ijäs, A. Uppstu, M. Ervasti, A. Harju, P. Liljeroth and I. Swart,
234. G. G. Odian, Principles of Polymerization, J. Wiley & Sons, Nature Commun., 2013, 4, 2023.
Hoboken, NJ, 2004. 265. H. Huang, D. Wei, J. Sun, S. L. Wong, Y. P. Feng, A. H. C. Neto
235. S. Setayesh, A. C. Grimsdale, T. Weil, V. Enkelmann, K. Müllen, and A. T. S. Wee, Sci. Rep., 2012, 2, 983.
F. Meghdadi, E. J. W. List and G. Leising, J Am Chem Soc, 2001, 266. P. Han, K. Akagi, F. Federici Canova, H. Mutoh, S. Shiraki, K.
123, 946. Iwaya, P. S. Weiss, N. Asao and T. Hitosugi, ACS Nano, 2014, 8,
236. J. Lee, H.-J. Cho, B.-J. Jung, N. S. Cho and H.-K. Shim, 9181.
Macromolecules, 2004, 37, 8523. 267. Y.-C. Chen, D. G. de Oteyza, Z. Pedramrazi, C. Chen, F. R.
237. M. G. Schwab, A. Narita, Y. Hernandez, T. Balandina, K. S. Mali, Fischer and M. F. Crommie, ACS Nano, 2013, 7, 6123.
S. De Feyter, X. Feng and K. Müllen, J Am Chem Soc, 2012, 134, 268. H. Zhang, H. Lin, K. Sun, L. Chen, Y. Zagranyarski, N. Aghdassi,
18169. S. Duhm, Q. Li, D. Zhong, Y. Li, K. Müllen, H. Fuchs and L. Chi,
238. M. El Gemayel, A. Narita, L. F. Dössel, R. S. Sundaram, A. J Am Chem Soc, 2015, 137, 4022.
Kiersnowski, W. Pisula, M. R. Hansen, A. C. Ferrari, E. Orgiu, X. 269. N. Abdurakhmanova, N. Amsharov, S. Stepanow, M. Jansen, K.
Feng, K. Müllen and P. Samori, Nanoscale, 2014, 6, 6301. Kern and K. Amsharov, Carbon, 2014, 77, 1187.
239. A. N. Abbas, B. Liu, A. Narita, L. F. Dössel, B. Yang, W. Zhang, 270. A. Basagni, F. Sedona, C. A. Pignedoli, M. Cattelan, L. Nicolas,
J. Tang, K. L. Wang, H. J. Räder, X. Feng, K. Müllen and C. M. Casarin and M. Sambi, J Am Chem Soc, 2015, 137, 1802.
Zhou, J Am Chem Soc, 2015, 137, 4453. 271. O. Endo, M. Nakamura, K. Amemiya and H. Ozaki, Surf. Sci.,
240. M. Saleh, M. Baumgarten, A. Mavrinskiy, T. Schäfer and K. 2015, 635, 44.
Müllen, Macromolecules, 2010, 43, 137. 272. C. Bronner, S. Stremlau, M. Gille, F. Brauße, A. Haase, S. Hecht
241. T. H. Vo, M. Shekhirev, D. A. Kunkel, M. D. Morton, E. and P. Tegeder, Angew. Chem. Int. Ed., 2013, 52, 4422.
Berglund, L. Kong, P. M. Wilson, P. A. Dowben, A. Enders and 273. Y. Zhang, Y. Zhang, G. Li, J. Lu, X. Lin, S. Du, R. Berger, X.
A. Sinitskii, Nat. Commun., 2014, 5, 3189. Feng, K. Müllen and H.-J. Gao, Appl. Phys. Lett., 2014, 105,
242. M. Saleh, PhD thesis, University of Mainz (Germany), 2010. 023101.
243. T. H. Vo, M. Shekhirev, A. Lipatov, R. A. Korlacki and A. 274. P. B. Bennett, Z. Pedramrazi, A. Madani, Y.-C. Chen, D. G. de
Sinitskii, Faraday Discuss., 2014, 173, 105. Oteyza, C. Chen, F. R. Fischer, M. F. Crommie and J. Bokor,
244. T. H. Vo, M. Shekhirev, D. A. Kunkel, F. Orange, M. J. F. Appl. Phys. Lett., 2013, 103, 253114.
Guinel, A. Enders and A. Sinitskii, Chem. Commun., 2014, 50, 275. C.-A. Palma, K. Diller, R. Berger, A. Welle, J. Björk, J. L.
4172. Cabellos, D. J. Mowbray, A. C. Papageorgiou, N. P. Ivleva, S.

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 27
 Chemical Society Reviews Page 28 of 28
ARTICLE Journal Name

Matich, E. Margapoti, R. Niessner, B. Menges, J. Reichert, X.

Feng, H. J. Räder, F. Klappenberger, A. Rubio, K. Müllen and J.
V. Barth, J Am Chem Soc, 2014, 136, 4651.
276. H. Sakaguchi, Y. Kawagoe, Y. Hirano, T. Iruka, M. Yano and T.
Nakae, Adv. Mater., 2014, 26, 4134.
277. A. V. Talyzin, I. V. Anoshkin, A. V. Krasheninnikov, R. M.
Nieminen, A. G. Nasibulin, H. Jiang and E. I. Kauppinen, Nano
Lett., 2011, 11, 4352.
278. A. Chuvilin, E. Bichoutskaia, M. C. Gimenez-Lopez, T. W.
Chamberlain, G. A. Rance, N. Kuganathan, J. Biskupek, U. Kaiser
and A. N. Khlobystov, Nat Mater, 2011, 10, 687.
279. T. W. Chamberlain, J. Biskupek, G. A. Rance, A. Chuvilin, T. J.
Alexander, E. Bichoutskaia, U. Kaiser and A. N. Khlobystov, ACS
Nano, 2012, 6, 3943.
280. H. E. Lim, Y. Miyata, M. Fujihara, S. Okada, Z. Liu, Arifin, K.
Sato, H. Omachi, R. Kitaura, S. Irle, K. Suenaga and H.
Shinohara, ACS Nano, 2015, 9, 5034.
281. S. Bandow, M. Takizawa, K. Hirahara, M. Yudasaka and S.
Iijima, Chem. Phys. Lett., 2001, 337, 48.

28 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 2012