Construction of 1D π-stacked superstructures with inclusion channels through symmetry-decreasing crystallization of discotic molecules of c 3 symmetry

Article abstract of DOI:10.1002/chem.201103133

Supramolecular architectures that possess both 1D π-stacked columns and inclusion channels were constructed by symmetry-decreasing crystallization of dehydrobenzo[12]annulene (DBA) derivatives with naphthyl arms and C₃ symmetry (see figure). Th

Full text of DOI:10.1002/chem.201103133

DOI: 10.1002/chem.201103133
Construction of 1D p-Stacked Superstructures with Inclusion Channels
through Symmetry-Decreasing Crystallization of Discotic Molecules of C3
Symmetry
Ichiro Hisaki,*[a] Hirofumi Senga,[a] Hajime Shigemitsu,[a] Norimitsu Tohnai,[a, b] and
Mikiji Miyata*[a]
A 1D p-stacked columnar assembly composed of discotic
p-conjugated molecules is one of the key architectures of or-
ganic semiconductor materials. To date, attractive proper-
ties, such as energy transfer and charge-carrier mobility,
have been reported for the architectures of polycyclic aro-
matic hydrocarbons, porphyrin, phtharocianine, and acety-
lene-bridged macrocycles.[1] In connection to this, we
became interested in construction of supramolecular archi-
tectures with both 1D p-stacked columns and inclusion
channels (abbreviated as 1D-pS-IC superstructure), because
optical and electrical properties of these 1D assemblies are
expected to be tuned by additional molecules accommodat-
ed in the channels, and moreover, absorption and desorption
of the molecules may lead to dynamic changes of the prop-
erties. The 1D-pS-IC superstructures have recently been
achieved in covalent organic frameworks (COF).[2–4]. On the
other hand, noncovalently linked 1D-pS-IC systems formed
through weak interactions are still rare,[5] although such sys-
tems are expected to show more dynamic structural change
and physical-property modulation compared with covalently
linked systems.
To generate inclusion spaces in a molecular assembly,
molecules with C3 symmetry are often applied,[6–9] because it
Figure 1. Schematic representation for construction of 1D, p-stacked, col-
is easy to image that they can give assemblies with hexago-
nal or trigonal void space (Figure 1a and b, respectively)
when they experience symmetry carry-over crystallization.[10]
Formation of these superstructures, however, are frequently
thwarted by offset-mannered stacking of the molecule that
does not give infinite channels, but discrete void spaces.[8]
umnar architectures with inclusion channels composed of a discotic mole-
cule with C3 symmetry: a) Hexagonal and b) trigonal arrangements
formed through symmetry carry-over crystallization. c) A layer-by-layer
arrangement with rhombic inclusion channels formed through a symme-
try-decreasing crystallization. The hierarchical scenario for a layer-by-
layer superstructure formation involves the following processes: i) forma-
tion of two-fold column, ii) layer formation by translational assembly of
the column, and iii) lamination of the layer accompanied by guest inclu-
sion into the space surrounded by the other arm.
[a] Dr. I. Hisaki, H. Senga, H. Shigemitsu, Dr. N. Tohnai,
Prof. Dr. M. Miyata
Therefore, herein, we planned to construct the 1D-pS-IC su-
perstructure by symmetry-decreasing crystallization of a C3
molecule with rigid aromatic arms in the periphery (Fig-
ure 1c). The term we propose—symmetry-decreasing crys-
tallization—denotes crystallization when high-symmetry
molecules adopt crystal structures with lower symmetry. A
scenario of the crystallization in this study is hierarchically
described as follows: i) Two C3 molecules form a two-fold
symmetric dimer so as to maximize their van der Waals con-
tacts provided by the core and two arms.[11] Subsequently,
Department of Material and Life Science
Graduate School of Engineering, Osaka University
2–1 Yamadaoka, Suita, Osaka 565-0871 (Japan)
Fax : (+81)6-6879-7406
E-mail: hisaki@mls.eng.osaka-u.ac.jp
miyata@mls.eng.osaka-u.ac.jp
[b] Dr. N. Tohnai
Japan Science and Technology Agency (JST)
PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 322-0011 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201103133.
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Chem. Eur. J. 2011, 17, 14348 – 14353

COMMUNICATION
the dimers stack to form a two-fold columnar assembly.
ii) The two-fold columns align to form a layer, which has
projecting arms as pillars on its surface. iii) The layers stack;
this is accompanied by guest inclusion into void spaces sur-
rounded by the pillars to form the 1D-pS-IC superstructure.
Discotic hexadehydrotribenzo[12]annulene (DBA)[12] with
C3 symmetry seems to be an appropriate compound for the
p-conjugated core, because a p-stacked 1D superstructure of
a DBA derivative was revealed to exhibit significant aniso-
tropic hole-carrier mobility along the columnar axis.[13] Fur-
thermore, DBA derivatives have been applied as building
blocks of various supramolecular architectures, including
vesicles,[14] columnar liquid crystals,[15] and porous 2D net-
works on a highly oriented pyrolytic graphite (HOPG) sur-
face.[16]
Herein, we first demonstrate that the 1D-pS-IC super-
structures of DBA derivatives with C3 symmetry are estab-
lished by symmetry-decreasing crystallization. Particularly,
2-naphthyl-armed DBA gave a framework that exhibited a
relatively wide channel with walls of the naphthyl plane.
The channel is capable of accommodating various aromatic
guests through CH–p or Cl–p contacts with the walls. Fur-
thermore, some crystals dynamically release the included
guest molecules even under ambient conditions, with accom-
panying structural changes.
tively) with a 1:1 host/guest molar ratio, and 1,5-dichloroan-
thracene (3·Cl2Ant) with a 2:1 host/guest ratio. In these
structures, coinstantaneous formation of both 1D stacked
DBA superstructures and 1D inclusion spaces were success-
fully achieved. Quinoline-armed DBAs 4 and 5, to our
dismay, did not yielded any inclusion crystals despite of
many trials;
4 formed a guest-free crystal (Figure S1,
Table S1 in the Supporting Information) and 5 has not yet
given any crystals, but amorphous materials.
In Figure 2, crystal structures of 1·CHCl3, 2·Tol, and 3·Tol
are shown. The 1·CHCl3 crystal exhibits a pseudo-two-fold
1D columnar structure of DBA along the a axis. The dimeric
column aligns along the diagonal direction of the bc plan to
give a layer, which stacks along the b axis, and a crystal with
1D-pS-IC superstructure (Figure 2a). The fact that only
chloroform molecules are accommodated in the narrow in-
clusion spaces surrounded by rotationally disordered phenyl
groups indicates that a phenyl group is too small as a pillar
to generate inclusion space. Naphthalene-armed DBAs 2
and 3, on the other hand, achieved obvious 1D-pS-IC super-
structures without disorder of the host frameworks. The
arms of DBA 2 are largely twisted from the DBA plane by
51.8–72.68 (Figure S2 in the Supporting Information) be-
cause of steric repulsion between the hydrogen atoms at
peri-positions of the naphthyl group and those of the DBA
ring. Therefore, the rhombic dimeric pair is not formed.
DBA 2 is slipped stacked with a small p overlap to form a
column. The columns align to form two types of narrow in-
clusion channels (A) and (B) with dimensions of approxi-
mately 3.7ꢁ4.3 and 6.8ꢁ3.1 ꢂ2, respectively (Figure 2b).
Contrary to the 1-naphthyl moieties in 2, the 2-naphthyl
groups in 3 are less hindered, and therefore, twisted from
the DBA plane with smaller angles of 1.7–32.68. Naphthyl
arms I and II take part in the widely spread edge-to-face
CH–p contact with the adjacent molecule (Figure 2c) to
form a two-fold helical column. The column aligns along the
c axis to form a layer, and the layer stacks along the a axis
to form an inclusion channel, with dimensions of approxi-
mately 5.2ꢁ9.0 ꢂ2, surrounded by the other naphthyl arm
(III). In the channels, toluene molecules are slipped stacked
in two rows.
DBAs 1–5 were synthesized according to Scheme 1. Re-
crystallization of the DBAs was performed in the presence
of various aromatic compounds to give inclusion crystals.[17]
Furthermore, we succeeded in revealing crystal structures
of 3·Xyl, 3·ClBen, 3·Cl2Ben, and 3·Cl2Ant, which have quite
similar porous frameworks with that of 3·Tol. However, re-
crystallization from toluene solution often yields a mixture
of 3·Tol and guest-free crystals. In the case of the o-xylene
solution, only small amounts of 3·Xyl was obtained as a
minor product, although a crystal structure of the guest-free
crystal was not revealed due to crystal size and mosaicity
(Figure S3 in the Supporting Information). On the other
hand, crystallization of 3 from chlorobenzene and dichloro-
benzene solutions uniquely yielded 3·ClBen and 3·Cl2Ben.
These results indicate that chloro-substituted benzene deriv-
atives are preferably included in the channels because of at-
tractive dispersion forces between the chlorine atoms of the
guest and the sp2-carbon atoms of the host (Cl–p interac-
tions),[18] in addition to CH–p interactions.[19] Figure 3 shows
Scheme 1. DBA derivatives with rigid aromatic arms and aromatic guests
included in 1D channels.
Contrary to the DBA crystals with the space groups of R3c
and R-3c, which we have reported previously,[8c] the present
systems gave crystal structures with lower symmetry.
Namely, DBA 1[8c] yielded a P-1 crystal that did not include
any aromatic molecules, but that did include chloroform
(1·CHCl3) with a 2:1 host/guest molar ratio. DBA 2, on the
other hand, gave a P-1 crystal that included toluene (2·Tol)
with a 1:1 host/guest molar ratio. DBA 3 gave P21/c crystals
that included toluene, o-xylene, chlorobenzene, and o-di-
chlorobenzene, (3·Tol, 3·Xyl, 3·ClBen, and 3·Cl2Ben, respec-
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I. Hisaki, M. Miyata et al.
Figure 2. Porous frameworks in the crystals of a) 1·CHCl3, b) 2·Tol, and c) 3·Tol. In the case of DBAs 1 (a) and 3 (c), the crystal structures can be inter-
preted with the use of the hierarchical scenario described in Figure 1. The guest molecules, that is, chloroform for (a), toluene for (b) and (c) in the chan-
nels are omitted for clarify. Carbon atoms of DBAs are colored in gray or dark gray for clarify. Two phenyl groups of DBA 1 in (a) are disordered. Geo-
metrical parameters, an angle between a mean plane of the DBA ring and the columnar axis and a distance between mean planes of the stacked DBA
rings are shown on the figures of the columns.
the inclusion channels of 3·Tol, 3·Xyl, 2·ClBen, 2·Cl2Ben,
and 3·Cl2Ant. The channels have a smooth surface without a
narrow bottle neck (the shortest width estimated by a 1.0 ꢂ
radius probe is ca. 8.6 ꢂ). Two walls of the rhombic chan-
nels are composed of the naphthalene plane, which is con-
venient to hold aromatic guest molecules through edge-to-
face interactions. In the crystals of 3·Tol and 3·Xyl, toluene
and o-xylene molecules interact perpendicularly with the
naphthalene walls through CH–p interactions; the dihedral
angles are 89.5 and 85.58, respectively. In the crystals of
3·ClBen and 3·Cl2Ben, the guest molecules interact perpen-
dicularly with the walls through Cl–p, as well as CH–p, in-
teractions; the dihedral angles are 89.5 and 85.58, respective-
ly. Because of the effective Cl–p contacts, the latter two in-
clusion crystals are well stabilized and are obtained exclu-
sively as described above. Furthermore, a larger p system,
1,5-dichloroanthracene, for which the molecular size approx-
imately consists of two coplanarly arranged chlorobenzene
molecules, is also accommodated in the channel successfully
(the dihedral angle between the naphthalene and anthra-
cene planes is 82.48).
Interestingly, the crystals that include highly volatile guest
molecules, that is, 3·Tol and 3·ClBen, spontaneously and
gradually release the guests from the channels, even at room
temperature. As shown in Figure 4a, freshly prepared crys-
tals of 3·Tol and 3·ClBen show gradual weight loss in the
thermal gravimetry (TG) curves at 358C; 3·Tol and 3·ClBen
lose 92 and 59% of the accommodated guest molecules
1
Figure 3. Inclusion-channels-accommodated, aromatic, guest molecules.
after 3.5 and 6.5 h, respectively. H NMR spectroscopy also
a) 1D channel in the 2·Tol crystal visualized by using a probe radius of
supports guest release: 87 and 67% losses for 3·Tol and
1.0 ꢂ. Packing diagrams are focused into the guest molecules: b) 3·Tol,
3·ClBen, respectively (Figure S5 in the Supporting Informa-
c) 3·Xyl, d) 3·ClBen, e) 3·Cl2Ben, and f) 3·Cl2Ant. Carbon and chlorine
atoms of the guests are in black and dark gray, respectively.
tion). This behavior is quite a contrast to our previous sys-
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Chem. Eur. J. 2011, 17, 14348 – 14353

1D, p-Stacked Superstructures with Inclusion Channels
COMMUNICATION
Figure 5. PXRD pattern changes of 3·Tol upon heating: a) before heating
(308C), at b) 70, c) 90, and d) 1108C, and e) after the sample had been
cooled down to 308C again.
lease of the guest molecules, a fluorescence spectrum of the
3·Tol crystal is slightly redshifted (Figure S9 in the Support-
ing Information). This indicates changes of the overlap be-
tween the DBA planes.
Figure 4. Spontaneous guest desorption of the crystals of 3·Tol and
3·ClBen at 358C accompanied by structural changes. a) Guest desorption
curves of 3·Tol (solid line) and 3·ClBen (dash line) obtained from TG
analysis. b) PXRD patterns of the crystals 3·Tol (i,ii) and 3·ClBen (iii,iv)
before (i,iii) and after (ii,iv) laying of the crystals at 358C for 4 and 7 h,
respectively.
In summary, we successfully prepared crystals that have
both 1D, p-stacked, columnar superstructure and 1D, contin-
uous, inclusion channel accommodating aromatic molecules.
Such structures were achieved by symmetry-decreasing crys-
tallization of discotic molecules with C3 symmetry, namely,
DBA derivatives with naphthyl arms. The sterically hin-
dered, rigid naphthalene group yields void spaces surround-
ed by walls that contain p planes. The guest molecules, tolu-
ene and o-xylene, are accommodated through CH–p con-
tacts in the channels. Furthermore, in the cases of chloro-
benzene, o-dichlorobenzene, and 1,5-dichloroanthracene,
Cl–p contacts stabilize guest accommodation. Based on this
result, halogen-substituted aromatic compounds with n-type
nature might be accommodated in the channels to construct
the crystal with the pathways for both electron and hole. We
also revealed that inclusion crystals with volatile guest mole-
cules experience spontaneous guest desorption under ambi-
ent conditions; this results in shrinkage of the cell. This
structural change induced a slight redshift of the fluores-
cence spectrum.
tems, which have discrete inclusion spaces that accommo-
dates guest molecules (Figure S6 in the Supporting Informa-
tion).[8c] Powder X-ray diffraction (l=1.541 ꢂ, PXRD) pat-
terns of 3·Tol and 3·ClBen indicate that guest release pro-
vided structural changes as shown in Figure 4b; new peaks
appear at 3.7, 6.5, 7.6, and 10.78 upon the guest release. This
structural change was also observed for 3·Cl2Ben in addition
to 3·Tol and 3·ClBen when the crystals were heated (Fig-
ure S7 in the Supporting Information). To perform a more
precise crystallographic analysis on the structure transforma-
tions, PXRD-pattern changes of 3·Tol were monitored by
using synchrotron X-ray diffraction (l=1.300 ꢂ) under
heating conditions. As shown in Figure 5, the peak at 2.848
that corresponds to the (100) plane disappeared, whereas
unambiguous peaks at 3.20, 6.40, 6.47, and 8.858 appeared.
These spectral changes coincide with those in Figure 4b.
The resulting pattern indicates that the a and b axes shrunk
by 2.87 and 0.13 ꢂ, respectively, whereas the c axis was
elongated by 0.42 ꢂ, and the b angle widened by 1.028, al-
though the crystalline lattice remains in space group P21/c,
as shown in Table S2 in the Supporting Information. Un-
fortunately, an exact crystal structure with satisfying quality
was not achieved by the Rietveld analysis. However, by con-
sidering the cell volume and molecular size of 3, the space
to accommodate a guest molecule was collapsed. Upon re-
The present study opens the door for a new category of
1D assemblies of discotic p molecules. A dynamic structural
change upon desorption and absorption of guest molecules
and guest-dependent physical properties, such as hole mobi-
lity, are now investigated in our laboratory.
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research (A
21245035), for Scientific Research on Innovative Areas (22108517), for
Challenging Exploratory Research (22651042) by MEXTACTHNUTRGNE(UNG Japan). We are
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14351

I. Hisaki, M. Miyata et al.
grateful to Dr. K. Miura, Dr. S. Baba, Dr. N. Mizuno, and Dr. K. Osaka
for crystallographic data collection at the BL38B1 (proposal No.
2009B1969 and 2010 A1427) and PXRD measurements at BL19B2 (pro-
posal No. 2010B1861 and 2010B1929) in the SPring-8, JASRI. I.H. thanks
FRC, Osaka University for funding. N.T. thanks JSPS for a Research Fel-
lowship for Young Scientists.
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2ACHTUGNTERN(UNG C42H24)·CAHTUNGTREN(NUNG CHCl3), Mw =1176.68, a=
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c=19.8688(9) ꢂ, a=100.0360(17)8, b=99.4874(18)8, g=95.561(3)8,
V=2080.89(14) ꢂ3, T=100 K, triclinic, space group P-1 (No. 2), Z=
2, dcalcd =1. 1.232 gcmÀ3, 34385 collected, 7990 unique (Rint =0.056)
reflections, the final R1 and wR2 values 0.092 (I>2.0s(I)) and 0.268
(all data), respectively. Crystal data for 3·Tol: (C54H30)·ACHTNURGTNEUNG(C7H8), Mw =
770.97, a=26.3124(4), b=5.24830(10), c=29.1901(5) ꢂ, a=908, b=
99.2125(6)8, g=908, V=3979.02(12) ꢂ3, T=100 K, monoclinic,
space group P21/c (No. 14), Z=4, dcalcd =1.287 gcmÀ3, 36354 collect-
ed, 10536 unique (Rint =0.080) reflections, the final R1 and wR2
values 0.076 (I>2.0s(I)) and 0.219 (all data), respectively. Crystal
data for 3·Xyl: (C54H30)·ACHTUNRTGEN(NUG C8H10), Mw =785.00, a=26.4700(4), b=
5.28000(10), c=29.1935(5) ꢂ, a=908, b=98.4027(6)8, g=908, V=
4036.33(12) ꢂ3, T=100 K, monoclinic, space group P21/c (No. 14),
Z=4, dcalcd =1.292 gcmÀ3, 28566 collected, 8433 unique (Rint =0.055)
reflections, the final R1 and wR2 values 0.065 (I>2.0s(I)) and 0.194
(all data), respectively. Crystal data for 3·ClBen: (C54H30)·ACHTUNGTRENNUNG(C6H5Cl),
Mw =791.39, a=26.1957(2), b=5.2068(1), c=29.2486(3) ꢂ, a=908,
b=99.0907(3)8, g=908, V=3939.28(5) ꢂ3, T=100 K, monoclinic,
space group P21/c (No. 14), Z=4, dcalcd =1.334 gcmÀ3, 32531 collect-
ed, 8788 unique (Rint =0.038) reflections, the final R1 and wR2
values 0.041 (I>2.0s(I)) and 0.111 (all data), respectively. Crystal
data for 3·Cl2Ben: (C54H30)·ACTHNUTGRENUNG(C6H4Cl2), Mw =825.83, a=26.5396(2),
b=5.1592(1), c=29.5302(3) ꢂ, a=908, b=98.8797(3)8, g=908, V=
3994.91(10) ꢂ3, T=100 K, monoclinic, space group P21/c (No. 14),
Z=4, dcalcd =1.373 gcmÀ3, 33252 collected, 9276 unique (Rint =0.043)
reflections, the final R1 and wR2 values 0.064 (I>2.0s(I)) and 0.191
(all data), respectively. Crystal data for 3·Cl2Ant
(C14H8Cl2)0.5 Mw =802.39, a=26.4636(3), b=5.12230(10), c=
29.4798(4) ꢂ, a=908, b=99.2825(5)8, g=908, V=3943.79(11) ꢂ3,
T=100 K, monoclinic, space group P21/c (No. 14), Z=4, dcalcd
: (C54H30)·-
A
,
=
1.351 gcmÀ3, 21301 collected, 8255 unique (Rint =0.095) reflections,
the final R1 and wR2 values 0.086 (I>2.0s(I)) and 0.249 (all data),
respectively. CCDC-846846 (1·CHCl3), CCDC-846847 (2·Tol),
CCDC-846848 (3·Tol), CCDC-846849 (3·Xyl), CCDC-846850
(3·ClBen), CCDC-846851 (3·Cl2Ben), and CCDC-846852 (3·Cl2Ant)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif.
[18] For reviews, see: a) G. R. Desiraju, T. Steiner, The Weak Hydrogen
Bond in Structural Chemistry and Biology, Oxford University Press,
Oxford, 1999; b) M. Nishio, CrystEngComm 2004, 6, 130–158; c) S.
Tsuzuki, A. Fujii, Phys. Chem. Chem. Phys. 2008, 10, 2584–2594.
14352
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ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 14348 – 14353

1D, p-Stacked Superstructures with Inclusion Channels
COMMUNICATION
[19] a) S. Tsuzuki, K. Honda, T. Uchimaru, M. Mikami, K. Tanabe, J.
Phys. Chem. A 1999, 103, 8265–8271; b) S. Tsuzuki, K. Honda, T.
Uchimaru, M. Mikami, K. Tanabe, J. Am. Chem. Soc. 2000, 122,
3746–3753; c) K. Shibasaki, A. Fujii, M. Mikami, S. Tsuzuki, J.
Phys. Chem. A 2007, 111, 753–758.
Received: October 5, 2011
Published online: November 23, 2011
Chem. Eur. J. 2011, 17, 14348 – 14353
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
14353