Hexagonal array formation by intermolecular halogen bonding using a binary blend of linear building blocks: STM study

Article abstract of DOI:10.1039/c9cc00532c

Hexagonal arrays were fabricated via intermolecular halogen bonding between two linear molecular building blocks in a bicomponent blend. The substitution position of the pyridine N atom involved in the halogen bond plays an important role in the formation

Full text of DOI:10.1039/c9cc00532c

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Kikkawa, M.
Nagasaki, E. Koyama, S. Tsuzuki and K. Hiratani, Chem. Commun., 2019, DOI: 10.1039/C9CC00532C.
This is an Accepted Manuscript, which has been through the
Volume 52 Number
1 4 January 2016 Pages 1–216
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Accepted Manuscripts are published online shortly after
Chemical Communications
www.rsc.org/chemcomm
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
=
3
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC00532C
ChemComm
COMMUNICATION
Hexagonal array formation by intermolecular halogen bonding
using a binary blend of linear building blocks: STM study
Yoshihiro Kikkawa,* Mayumi Nagasaki, Emiko Koyama, Seiji Tsuzuki and Kazuhisa Hiratani
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Hexagonal arrays were fabricated via intermolecular halogen networks
bonding between two linear molecular building blocks in a tris(ethynylpyridyl)benzene
using
a
binary
and
blend
1,3,5-trifluoro-2,4,6-
of
1,3,5-
bicomponent blend. The substitution position of the pyridine N triidobenzene; they emphasized that electrical stimulus was
atom involved in the halogen bond plays an important role in the important to induce the formation of the 2D networks via
formation of the hexagonal structures.
halogen bonding.7k However, to the best of our knowledge,
there have been no reports of the formation of honeycomb
structures through halogen bonding using a bicomponent blend
of linear building blocks without C3 symmetry.
Halogen bonds, which form between electrophilic halogen
atoms and nucleophilic atoms such as those with lone pairs, are
highly directional interactions with strengths comparable to
those of hydrogen bonds.1 Halogen bonds are generally
described as R-X···Y, where X is a halogen atom covalently linked
to the R group, the three dots represent the halogen bond, and
Y is the halogen bond acceptor. The magnitude of the halogen
bond is mainly controlled by the electrostatic interaction of the
halogen atom, and follows the order Cl < Br < I.2 Halogen bonds
are known to play important roles in the formation of
supramolecular structures in artificial and biological systems.3
The formation of hexagonal arrays on a solid substrate has
been achieved using C3-symmetric molecular building blocks
with rigid molecular frameworks, and their structures have
been revealed using scanning tunnelling microscopy (STM) at
molecular resolution.4 The hexagonal spaces have been utilized
as templates to accommodate guest molecules.5 De Feyter and
In this contribution, we prepared compounds 1 and 2, which
contain lone pairs and halogen atoms as halogen bonding sites,
respectively (Chart 1). The compounds p1 and m1, which varied
only in the pyridine substitution position, were prepared to
study the effect of the substitution position on the formation of
the 2D structure via halogen bonding. The 2D structure of each
component was studied using STM at the highly oriented
pyrolytic graphite (HOPG)/1-phenyloctane interface. Then, the
STM observations were performed for bicomponent blends of
m1 and p1 with 2 (1:1 ratio). In addition, the intermolecular
interactions between 1 and 2 were studied through DFT
calculations using the program Gaussian 09.8
Tobe
et
al.
prepared
rigid
and
C3-symmetric
dihydrobenzo[12]annulenes to construct porous hexagonal
networks through the interdigitation of the alkyl chains, and
studied the formation of the hexagonal structures, pore size
tuning, chiral assemblies, and guest incorporation into the
hexagonal pores for host-guest chemistry.6
The construction of molecular assemblies through halogen
bonding has attracted increasing attention.7 For example, Wan
et al. demonstrated the formation of 2D hexagonal porous
Chart 1 Chemical structures of compounds 1, 2, and 3 prepared in this study.
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba
Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Electronic Supplementary Information (ESI) available: Experimental detail,
additional STM images, lattice constants, molecular models, and statistical analysis
of 2D structure formation. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
Chem. Commun., 2018, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
separated by regular dark troughs, which were attributed to the
View Article Online
DOI: 10.1039/C9CC00532C
alkyl chain units (L5 = 2.07 ± 0.22 nm, Fig. 2A). The bright
columns were composed of short stick-like parallel structures.
Taking the I···N halogen bond into account, the short sticks were
attributed to the -conjugated unit of p1 and the two aromatic
rings of 2, one of which was functionalized with halogens while
the other possessed alkyloxy chains (Fig. S2, ESI). DFT
calculations (Fig. S3, ESI) suggested that pairs of p1 and 2
molecules were arranged periodically, with neighbouring p1/2
pairs having opposite orientations due to Ar-F···H-Py
interactions between neighbouring pairs in addition to the
halogen bond within each pair. The proposed molecular model
is shown in Fig. 2B. Due to the close packing of the bright stick-
like structures comprising the columns, there was not enough
space for all the alkyl chains to be accommodated in the lattice.
Thus, only one of the two alkyloxy chains of each p1 and 2 unit
was attached to the HOPG surface; the other alkyl chain was not
adsorbed on the substrate, but instead was directed towards
the solvent phase.
Fig. 1 STM images of p1, m1 and 2 (1 mM) physisorbed at the HOPG/1-phenyloctane
interface. Molecular models are superimposed on the STM images. A set of arrows
indicates the HOPG lattice directions. Tunnelling conditions: (A) I = 1.3 pA, V = -566 mV,
(B) I = 2.0 pA, V = -390 mV, (C) I = 1.0 pA, V = -566 mV.
First, the 2D structures of the mono-component systems
were observed using STM at the HOPG/1-phenyloctane
interface. Fig. 1A shows the STM image of p1, which formed
columns consisting of two parallel bright lines that were
sandwiched between dark troughs with a width L1 of 2.07 ± 0.13
nm. The L1 value was identical to the length of the octadecyl
chain (2.16 nm; Fig. 1A). The bright and dark contrast areas
corresponded to the -conjugated motif and octadecyl chains
in p1, respectively. A molecular model was developed, and is
superimposed on the STM image. The para-substituted pyridine
moieties were oriented in a face-to-face manner, and the alkyl
chain pairs of the molecules were arranged side-by-side;
neighbouring molecules were orientated in opposite directions.
The lattice constants of the 2D structures are summarized in
Table S1 (ESI).
A similar 2D structure was found for m1; namely, a double
columnar structure was formed, as shown in Fig. 1B. The
alternating arrangement of the neighbouring alkyl chain units
(L2 = 2.06 ± 0.20 nm) was also found in the physisorbed m1
monolayer. From Fig. 1A and 1B, it can be concluded that the
substitution position of pyridine in 1 does not significantly
influence 2D structure formation, as p1 and m1 formed nearly
identical 2D structures.
A single-line columnar structure was observed for 2, and is
shown in Fig. 1C. The 3,5-alkyloxy chains of each molecule were
not parallel to one another, but instead assumed an expanded
conformation with an angle of 119 ± 6° to maximize the
dispersion forces between neighbouring molecules. The alkyl
chains thus formed a herringbone structure with lengths of L3 =
2.21 ± 0.14 nm and L4 = 2.33 ± 0.19 nm, and the direction of the
iodine atom of 2 alternated in adjacent columns. It is
noteworthy that the 2D structures of p1, m1, and 2 were not
affected by the concentration of the 1-phenyloctane solution
within the range of 62.5 µM–2 mM, i.e. there was no
concentration effect on the 2D structure in these mono-
component systems.
After study of the mono-component systems, binary blends
were prepared, expecting I···N halogen bonding,3 which
produced supramolecular 2D assemblies that were different
from those of 1 and 2. The effect of the pyridine substitution
position on the 2D structure formation was examined using
bicomponent blends of m1 and p1 with 2.
Fig. 2 shows the STM image of the bicomponent blend of p1
and 2 (0.125 mM) observed at the HOPG/1-phenyloctane
interface.9 Parallel linear columns with bright contrast were
Fig. 2 STM image of the bicomponent blend of p1 and 2 observed at the HOPG/1-
phenyloctane interface (A). A set of arrows indicates the HOPG lattice directions. Panel
(B) shows the proposed molecular model based on the STM images and DFT calculation
(Fig. S3, ESI) and the geometry of the I···N halogen bond. Tunnelling conditions: I = 1.3
pA, V = -800 mV.
Of particular interest is the formation of hexagonal arrays by
the bicomponent blend of m1 and 2 (1 mM), shown in Fig. 3A.
The m-substitution of the m1 pyridine allowed the arrangement
of the 2 units at an angle of ca. 120° via the I···N halogen
bonding (Fig. 3B). The halogen bonds and the Ar-F···H-Py
interactions among three pairs of 2 and m1 molecules (Fig. S4,
ESI) formed triangular helical assemblies; the alkyl chains of
these assemblies associated to surround hexagonal pores (L6 =
L7 = 2.16 ± 0.19 nm). In the proposed model shown in Fig. 3B,
the alkyl chains of m1 were aligned parallel to one another,
whereas those of 2 were expanded, as evidenced by the highly
resolved STM images in Figs. 3C, 3D, and S5 (ESI). It is
noteworthy that the binary blend of m1 and compound 3,10
which was the 3,4-alkyloxy substituted analogue of 2, did not
show a hexagonal structure, but instead displayed only the
double columnar structure originating from m1 under the
present experimental conditions. This result suggests that the
3,5-dialkyloxy substitution in 2 is indispensable for the
formation of a hexagonal structure in the present bicomponent
blend system, possibly due to the preorganization of the alkyl
chains along the two sides of a hexagonal framework.
2 | Chem. Commun., 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
ChemComm
Please do not adjust margins
Journal Name
Several groups have reported that 2D chirality can be
COMMUNICATION
At a concentration of 1 mM, linear structures were also
View Article Online
DOI: 10.1039/C9CC00532C
introduced and expressed by even achiral molecule assemblies observed in addition to the hexagonal ones, as shown in Fig. S8
on a surface.11 Careful analysis of the STM images revealed (ESI). These linear structures corresponded to those observed
clockwise (CW) and counter-clockwise (CCW) helical triangular for the mono-component systems of m1 and 2. It has been
structures, as shown in Fig. S7 (ESI). This result suggests that the reported that the concentration of the components in the
chirality in the 2D structure was induced by the different solution sometimes affects 2D structure formation at the
orientations of the halogen-bonded pairs of the linear solid/liquid interface, and that the molecular density on the
molecules m1 and 2. At the centre of the honeycomb structure, surface increases with an increase in the solution
molecules of the solvent 1-phenyloctane may have dynamically concentration.12 Thus, the effect of the concentration of the
filled the vacant space to stabilize the 2D structure.
premixed solution on the 2D structure was investigated for the
bicomponent blend of m1 and 2. Fig. S9 (ESI) shows wide-area
STM images of the bicomponent blend at different
concentrations. At the highest concentration, the linear
structures were predominant, whereas at lower concentrations,
the area of the linear structures decreased, and the population
of hexagonal arrays increased. The areas of the honeycomb and
linear structures at different concentrations were evaluated
from ten 200 nm × 200 nm STM images, and the resulting ratios
are shown in Fig. S10 (ESI). Although some areas displayed
unstable structures which could not be distinguished as either
hexagonal or linear domains, essentially, the lower the
concentration of the solution, the larger the population of
hexagonal arrays. For the lowest concentration examined (62.5
µM), hexagonal structures and unstable domains each occupied
about half the surface, and the blurred contrast observed for
the unstable domains may have been due to the presence of
low density and unstable molecular assemblies on the HOPG
surface.
In previous studies, halogen-bonded 2D networks
composed of I···N interactions were prepared either by simply
mixing the solutions of constituents7f or by the instantaneous
pulsed current applied between the substrate and the STM
tip.7k In our present study, the hexagonal arrays were effectively
formed by adjusting the concentration of the pre-mixed
solution, with greater numbers of honeycomb structures being
observed on the HOPG surface at low concentrations. The
molecular density of the 2D structures in m1 and 2 was
calculated from the lattice constants to be 0.32 and 0.29
molecule/nm2, respectively. In contrast, the molecular density
of the honeycomb structure in the bicomponent blend (m1+2)
was 0.12 molecule/nm2 (per one of the constituents). Therefore,
we propose that the low concentration of the building blocks
resulted in the reduced molecular density of the 2D structure
on the surface, allowing the preferential formation of
honeycomb structures: the triangular helical assemblies were
formed at the vertices of the hexagon via both halogen bonding
and Ar-F···H-Py interactions. In addition, the expanded
orientation of the alkyl chains in 2 guided the arrangement of
the m1 alkyl chains to surround a hexagonal pore, resulting in
the formation of supramolecular honeycomb structure
frameworks on the surface.
Fig. 3 (A) STM image of the bicomponent blend of m1 and 2 (1 mM) at the HOPG/1-
phenyloctane interface, and (B) the proposed molecular model based on the STM images
and DFT calculation (Fig. S4, ESI). Due to the meta substitution of pyridine and the
halogen bond, the angle between m1 and 2 was ca. 120°. (C) Highly resolved STM image
of the hexagonal arrays, on which the molecular model of a triangular helical assembly
with alkyl chains was superimposed; in (D) the building blocks 2 are highlighted in blue
and red. The expanded orientation of the alkyl chains of 2 is evident from the STM image,
and the orientation of m1 is shown in Fig. S4 (ESI). Note that panels (A, B) and (C, D) are
chiral (see. Fig. S7, ESI). A set of arrows indicates the HOPG lattice directions. Tunnelling
conditions: (A) I = 1.0 pA, V = -650 mV, (C) I = 2.0 pA, V = -353 mV.
In summary, double columnar (p1 and m1) and single-line
columnar structures (2) were observed in the mono-component
systems, by using STM at the HOPG/1-phenyloctane interface.
Formation of I···N halogen bonding allowed the construction of
supramolecular complexes on the surface. The short and stick-
like objects formed between p1 and 2 via halogen bond aligned
This journal is © The Royal Society of Chemistry 20xx
Chem. Commun., 2018, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
5
6
7
J. Teyssandier, S. De Feyter and K. S. Mali, Chem. Commun.,
2016, 52, 11465, and the references cited thereVinie.w Article Online
Y. Tobe, K. Tahara and S. De Feyter, BuDll.OCI:h1e0m.10.3S9o/cC.9JCpCn0.,0250312C6,
89, 1277, and the references cited therein.
in a parallel fashion to create a linear structure different from
those of the single component systems. Hexagonal arrays could
be efficiently fabricated in the mixture of m1 and 2, despite the
linear molecular building blocks. Cooperative I···N halogen
bonding and Ar-F···H-Py interactions formed triangular helical
assemblies. In addition, the preorganization of the alkyl chains
in 2 assisted the orientation of those of m1 along the hexagonal
framework, resulting in the formation of fascinating
honeycomb structures. Effective fabrication of the honeycomb
structures was achieved by tuning the concentration of the
blend solution, and lower concentrations were found to
increase the area over which the hexagonal arrays were formed.
The present study provided a rational method to construct
hexagonal arrays composed of a bicomponent blend of two
linear molecular building blocks via intermolecular halogen
bonding. We believe that supramolecular complex formation
induced by the directional halogen bonding contributes to the
development of molecular assembly techniques, and should be
applicable to the efficient production of nano-architectures and
their regular arrangement on a surface.
(a) A. Vanderkooy and M. S. Taylor, J. Am. Chem. Soc., 2015,
137, 5080; (b) H. L. Nguyen, P. N. Horton, M. B. Hursthouse,
A. C. Legon and D. W. Bruce, J. Am. Chem. Soc., 2004, 126, 16;
(c) M. Kondo, K. Okuomoto, S. Miura, T. Nakanishi, J. Nishida,
T. Kawase and N. Kawatsuki, Chem. Lett., 2017, 46, 1179; (d)
F. Wang, N. Ma, Q. Chen, W. Wang and L. Wang, Langmuir,
2007, 23, 9540; (e) F. Silly, J. Phys. Chem. C, 2013, 117, 20244;
(f) A. Mukherjee, J. Teyssandier, G. Hennrich, S. De Feyter and
K. S. Mali, Chem. Sci., 2017, 8, 3759; (g) Z. Guo, P. Yu, K. Sun,
S. Lei, Y. Yi and Z. Li, Phys. Chem. Chem. Phys., 2017, 19, 31540;
(h) B. Zha, X. Miao, P. Liu, Y. Wu and W. Deng, Chem. Commun.,
2014, 50, 9003; (i) Y. Makoudi, M. Beyer, J. Jeannoutot, F.
Picaud, F. Palmino and F. Chérioux, Chem. Commun., 2014, 50,
5714; (j) D. Peyrot and F. Silly, ACS Nano, 2016, 10, 5490; (k)
Q.-N. Zheng, X.-H. Liu, T. Chen, H.-J. Yan, T. Cook, D. Wang, P.
J. Stang and L.-J. Wan, J. Am. Chem. Soc., 2015, 137, 6128.
(a) Gaussian 09, Revision C01, M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G.
Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H.
Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J.
Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery Jr., J.
E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N.
Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi,
M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross,
V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A.
Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,
Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox,
Gaussian, Inc., Wallingford CT, 2009; (b) Details of the
computational methods are provided in the ESI.
8
This work was partly supported by the JSPS KAKENHI
(17K05851). We thank Dr. Hiroaki Sato and Dr. Thierry Fouquet
for the HR-MALDI-MS analysis.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
(a) G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimagi,
G. Resnati and G. Terraneo, Chem. Rev., 2016, 116, 2478; (b)
R. Tepper and U. S. Schubert, Angew. Chem. Int. Ed., 2018, 57,
6004.
9
It was difficult to obtain clear STM images at concentrations
higher than 0.125 mM. In some cases, double columnar
structures possibly composed of p1 were found as separated
domains, in addition to the major 2D structure in Fig. 2, as
shown in Fig. S1 (ESI).
2
3
(a) S. Tsuzuki, A. Wakisaka, T. Ono and T. Sonoda, Chem. Eur.
J., 2012, 18, 951; (b) S. Tsuzuki, T. Uchimaru, A. Wakisaka, T.
Ono and T. Sonoda, Phys. Chem. Chem. Phys., 2013, 15, 6088.
(a) E. Persch, O. Dumele and F. Diederich, Angew. Chem. Int.
Ed., 2015, 54, 3290; (b) L. C. Gilday, S. W. Robinson, T. A.
Barendt, M. J. Langton, B. R. Mullaney and P. D. Beer, Chem.
Rev., 2015, 115, 7118.; (c) J. Poznański, M. Winiewska, H.
Czapinska, A. Poznańska and D. Shugar, Acta Biochim. Pol.,
2016, 63, 203; (d) B. Li, S.-Q. Zang, L.-Y. Wang and T. C. W. Mak,
Coord. Chem. Rev., 2016, 308, 1.;
(a) R. Gutzler, T. Sirtl, F. Dienstmaier, K. Mahata, W. M. Heckl,
M. Schmittel and M. Lackinger, J. Am. Chem. Soc., 2010, 132,
5084; (b) T. Chen, G.-B. Pan, H. Wettach, M. Fritzsche, S. Höger,
L.-J. Wan, H.-B. Yang, B. H. Northrop, and P. J. Stang, J. Am.
Chem. Soc., 2010, 132, 1328; (c) D. Bléger, D. Kreher, F.
Mathevet, A.-J. Attias, G. Schull, A. Huard, L. Douillard, C.
Fiorini-Debuischert and F. Charra, Angew. Chem. Int. Ed., 2007,
46, 7404; (d) R. Gutzler, S. Lappe, K. Mahata, M. Schmittel, W.
M. Heckl and M. Lackinger, Chem. Commun., 2009, 680; (e) S.
Wu, S. Xu, Y. Geng, Z. Liu, H. Nie, L. Shu, K. Deng, Q. Zeng and
C. Wang, J. Phys. Chem. C, 2016, 120, 12618.; (f) Z. Ma, Y.-Y.
Wang, P. Wang, W. Huang, Y.-B. Li, S.-B. Lei, Y.-L. Yang, X.-L.
Fan and C. Wang, ACS Nano, 2007, 1, 160; (g) M. O. Blunt, J. C.
Russell, M. del C. Gimenez-Lopez, N. Taleb, X. Lin, M. Schröder,
N. R. Champness and P. H. Beton, Nat. Chem., 2010, 3, 74; (h)
C.-A. Palma, M. Bonini, A. Llanes-Pallas, T. Breiner, M. Prato,
D. Bonifazi, and P. Samorì, Chem. Commun., 2008, 5289.
10 The compound 3 could form the self-assembled 2D structure,
as shown in Fig. S6 (ESI).
11 (a) N. Katsonis, H. Xu, R. M. Haak, T. Kudernac, Ž. Tomović, S.
George, M. Van der Auweraer, A. P. H. J. Schenning, E. W.
Meijer, B. L. Feringa and S. De Feyter, Angew. Chem. Int. Ed.,
2008, 47, 4997; (b) S. Lei, M. Surin, K. Tahara, J. Adisoejoso, R.
Lazzaroni, Y. Tobe and S. De Feyter, Nano Lett., 2008, 8, 2541;
(c) J. A. A. W. Elemans, I. De Cat, H. Xu and S. De Feyter, Chem.
Soc. Rev., 2009, 38, 722; (d) T. Chen, W. H. Yang, D. Wang and
L. J. Wan, Nat. Commun., 2013, 4, 1389; (e) S. Yagai, M. Suzuki,
X. Lin, M. Gushiken, T. Noguchi, T. Karatsu, A. Kitamura, A.
Saeki, S. Seki, Y. Kikkawa, Y. Tani and K. I. Nakayama, Chem.
Eur. J., 2014, 20, 16128.
12 (a) S. Lei, K. Tahara, F. C. De Schryver, M. Van der Auweraer,
Y. Tobe and S. De Feyter, Angew. Chem. Int. Ed., 2008, 47,
2964; (b) N. Thi Ngoc Ha, T. G. Gopakumar and M. Hietschold,
J. Phys. Chem. C, 2011, 115, 21743; (c) A. Ciesielski, P. J.
Szabelski, W. Rżysko, A. Cadeddu, T. R. Cook, P. J. Stang and P.
Samorì, J. Am. Chem. Soc., 2013, 135, 6942; (d) S. Zhang, J.
Zhang, K. Deng, J. Xie, W. Duan and Q. Zeng, Phys. Chem. Chem.
Phys., 2015, 17, 24462; (e) L. Xu, X. Miao, L. Cui, P. Liu, K. Miao,
X. Chen and W. Deng, J. Phys. Chem. C, 2015, 119, 17920; (f)
V. Stepanenko, R. Kandanelli, S. Uemura, F. Würthner and G.
Fernández, Chem. Sci., 2015, 6, 5853. (g) F. Silly, J. Phys. Chem.
C, 2017, 121, 10413.
4
4 | Chem. Commun., 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC00532C
Graphical abstract
A bicomponent blend of linear building blocks leads to intermolecular halogen bonding,
resulting in the formation of hexagonal arrays.