Selenacalix[4]dithienothiophene: Synthesis, Structure, and Complexation of a Cyclic Tetramer of Selenide-Bridging Dithienothiophene

Article abstract of DOI:10.1002/asia.201801105

An efficient cyclization toward a cyclic tetramer of dithienothiophene (DTT) linked by divalent selenium atoms has been developed via palladium-catalyzed coupling reaction of (nBu₃Sn)₂Se. X-ray analysis revealed its highly symmetrical structure had an alternate arrangement of DTT units. There are several Se???π interactions forming a supramolecular network leading to large void channel space. The cyclic tetramer possesses moderate electron-donating ability. Furthermore, the cyclic tetramer undergoes complexation with C₆₀ in a 1:2 ratio in the solid state to give a highly symmetrical three-dimensional array of C₆₀.

Full text of DOI:10.1002/asia.201801105

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Selenacalix[4]dithienothiophene: Synthesis, Structure, and
Complexation of A Selenide-Bridged Dithienothiophene Cyclic
Tetramer
Authors: Masashi Hasegawa, Kazuhiro Takahashi, Ryota Inoue, Shiori
Haga, and Yasuhiro Mazaki
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To be cited as: Chem. Asian J. 10.1002/asia.201801105
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Selenacalix[4]dithienothiophene: Synthesis, Structure, and
Complexation of A Cyclic Tetramer of Selenide-Bridging
Dithienothiophene
Masashi Hasegawa*, Kazuhiro Takahashi, Ryota Inoue, Shiori Haga, Yasuhiro Mazaki
Dedication ((optional))
Abstract: An efficient cyclization toward
a
cyclic tetramer of
attractive because they can provide enhanced dimensionality
with a large host cavity, leading to a molecular assembled
porous materials.[11] However, while a wide variety of sulfur-
linked macrocycles based on π-framework unit have been
successfully prepared, there are few examples of selenium–
linked macrocyclic compounds because of the lack of efficient
cyclization method.[12] In 2014, Balakrishna and co-workers
dithienothiophene (DTT) linked by divalent selenium atoms has been
developed via palladium-catalyzed coupling reaction of (nBu3Sn)2Se.
X-ray analysis revealed its highly symmetrical structure having
alternate arrangement of DTT units. There are several Se••π
interactions to form a supramolecular network leading to large void
channel space. The cyclic tetramer possesses moderate electron-
donating ability. Furthermore, the cyclic tetramer undergoes
complexation with C60 in 1:2 ratio in the solid state to give highly
symmetrical three-dimensional array of C60.
prepared selenacalix[n]thiophenes (n
= 4–6) via aromatic
electrophilic substitution with SeCl2.[12a] In that case, only
electron-donating thiophene could undergo the cyclization with
Se atoms. In addition, HCl was produced during the reaction,
and it could be harsh conditions while the substitution reaction
proceeded. With this in mind the accessibility to Se-containing
cyclic compounds, we envisage that the coupling reaction of tin-
selenide, (nBu3Sn)2Se,[13] and appropriate aryl-dibromide leads
to the cyclic compound (3). In this communications, we disclose
In past few decades, cyclic oligothiophenes and their analogues
have fascinated many chemists in various fields.[1,2] A number of
two-dimensional planar oligothiophenes linked by π-conjugated
spacers have been so far developed owing to their promising
application for material science as well as their fundamental
scientific interests.[3] On the contrary, the preparation of
oligothiophenes has been studied to a lesser extent in three-
dimensional (3D) architecture, although they can offer novel
features that can not obtained from planar structure.[4]
a
facile cyclization reaction of a DTT derivative to give
selenacalix[4]DTT under Migita-Kosugi conditions. The solid-
state structure having large porous channels with large guest-
accessible void space is presented. Furthermore, we found that
selenacalix[4]DTT forms 1:2 complex with C60.
Thiacalix[4]thiophenes (1), which consist of four sets of
thienylene units and sulfide linkers, are cyclic thiophene
oligomers (Figure 1).[5] The combination of the aromatic subunits
and divalent angular –S– bonds renders the molecular structure
non-planar geometry. Recently, we reported a one-pot approach
for such cyclic compounds from a simple a precursor of
thiophene or dithieno[3,2-b:2’,3’-d]thiophenes (DTTs) derivatives
with (nBu3Sn)2S.[6,7] Palladium catalyzed coupling under Migita-
Kosugi conditions[8] successfully led to the thiacalix[4]thiophene
(1) or -DTT (2) in high yield, respectively. This result motivates
us to synthesize 3D macrocycles linked by other heteroatoms, in
particular selenium-linked cyclic compounds.
R
S
E
R
R
R
S
R
S
S
S
S
S
R
R
S
R
S
E
S
S
S
S
E
S
R
R
S
R
R
S
R
S
R
S
R
S
E
R
Thiacalix[4]thiophene (1)ꢀ
2 (E = S, R = TMS), 3 (E = Se, R = TMS) ꢀ
Organoselenium compounds have received considerable
attention because of their potential application not only for key
intermediates in organoselenium chemistry but also for building
block in biologically active molecules and pharmaceuticals.[9] In
addition, thanks to the large van der Waals radius of Se,
supramolecular three-dimensional network can be formed in the
solid state.[10] This packing force contributes to well-ordered
network that can be conductive organic materials having
possible hole/electron transporting properties. Therefore,
selenicalix[n]thiophene and its derivatives are particularly
Figure 1. Molecular structures of thiacalix[4]thiophene and its DTT derivatives
1–3.
The coupling reaction to form biaryl selenides (Ar-Se-Ar)
using (nBu3Sn)2Se was first developed by Nishiyama and co-
workers.[14] However, they only reported the coupling of
iodobenzene as the starting material in low yield. Therefore, we
first optimized the reaction conditions and examined its diversity
prior to the cyclization reactions (Table 1 and Figure S1). Initially,
we carried out with the coupling reaction of 4-iodo, 4-bromo-,
and 4-chlorotoluene in various conditions. When 4-iodotoluene
reacts with (nBu3Sn)2Se in the presence of Pd(PPh3)4 at 60 °C in
toluene, compound 4 was afforded in 91 % as isolated yield
(entry 1). However, compound 4 was formed in lower yield when
the reaction carried out at higher temperature (entry 2). In this
condition, diphenyl selenide (Ph2Se) and phenyl(p-tolyl)selenide
((p-tol)-Se-Ph) were obtained as major products, whose phenyl
[a]
Dr. M. Hasegawa, K. Takahashi, R. Inoue, S. Haga, Y. Mazaki
Department of Chemistry, Graduate School of Science
Kitasato University, 1-15-1 Kitasato
Minami-ku, Sagamihara, Kanagawa 252-0373 (Japan)
E-mail: masasi.h@kitasato-u.ac.jp
Supporting information for this article is given via a link at the end of
the document.
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ring(s) was/were originated from PPh3 on the catalyst. Similar
exchange was occasionally found in the previous literature when
the coupling reaction was carried out at higher temperature.[15]
On the contrary, better yield was obtained even at higher
temperature when we carried out with 4-bromotoluene (entry 4).
When we applied this condition to a variety of aryl halide as the
starting compounds, we obtained several biaryl selenide in good
yield (80-99 %) (Figure S1).
exists the improper rotation axis at the center of the molecule.
Four DTT rings adopt zig-zag geometry to avoid a steric
repulsion of TMS groups at the neighboring unit, and thence 3
forms
a
1,3-alternate geometry if compared as
a
selenacalix[4]arene analogue. The DTT walls in the 1,3-alternate
geometry results in a large cavity, and its size is determined
from the distance between S(1) and S(3) at the opposite sides to
be ca. 8.6 Å .
Table 1. Palladium-Catalyzed Reaction of Ar–X with (nBu3Sn)2Se [a]
(a)ꢀ
(b)ꢀ
X
Se
(nBu3Sn)2Se
S(1)ꢀ
S(3)ꢀ
Pd(PPh3)4
toluene
(X = Cl, Br, I)
4
Entry
X
I
Temp. (°C)
60
Time (h)
Yield (%) [b]
1
2
3
4
5
3
3
91
13
0
(d)ꢀ
I
120
(c)ꢀ
I
25
72
3
Br
120
84
3.577Åꢀ
Seꢀ
Cl
120
72
0
8.6 Å ꢀ
[a]
Conditions: p-tol-X (2.0 mmol), (nBu3Sn)2Se (1.0 mmol), Pd(PPh3)4
Cꢀ
(0.10 mmol), and toluene (2 mL). [b] Isolated yield.
As expected, the coupling of 2,5-dibromo-DTT derivatives
6[16] with (nBu3Sn)2Se proceeded smoothly to form the cyclic
products. Compound 3 was afforded in 29% yield after gel
permeation chromatography (GPC) separation (Scheme 1). In
sharp contrast to give various size of cyclic product in the case
of (nBu3Sn)2S used, only cyclic tetramer together with acyclic
compounds were observed. It presumably suggests that the
narrower angle of C–Se–C compared to that of C–S–C disfavor
to form larger cyclic products more than tetramer. Compound 3
was isolated as a stable pale yellow solid, and the molecular
structure was fully characterized by ESI-MS, NMR (1H, 13C, and
77Se), IR, and HRMS. The formation of cyclic tetramer was
confirmed by ESI-MS with a parent ion peak corresponding to
C56H72S12Se4Si8. The 1H and 13C NMR spectra revealed a highly
symmetrical structure, confirming the uniformity of all DTT-Se
units. The 77Se NMR spectrum contains only one signal owing to
the Se linkers at 346.8 ppm, exhibiting a typical chemical shift of
divalent diaryl selenide.
Figure 2. (a) ORTEP drawing of 3 with thermal ellipsoids shown at the 50%
level. (b) A quadrilateral geometry of 3. (c) Intermolecular Se•••π interactions.
(d) Large void cavity in the packing diagram
In the packing diagram, a repetitive porous structure was
formed through self-complementary Se•••π interactions (Figure
2c). Such a supramolecular network did not observed in other
thiacalix[4]thiophene systems, and hence the incorporating of
selenium atoms at the corner can reinforce the porous sheet in
the crystal (Figure 2d). Some residual electron densities, which
may be attributed to disordered chlorobenzene, are found in the
void space between the molecules in the c-axis direction. The
analysis of the void space suggested that the solvent-free
tetragonal crystal derived from the present crystal structure has
one-dimensional nano porous array with a large void volume of
2506 Å3 within a unit cell (10097 Å3) (Figure 3). This porous
feature implies potential application for guest-inclusion materials
based on cavity-assembled porous (CAP) materials.[11]
TMS
Br
TMS
Br
S
S
(nBu3Sn)2Se
ref. 16
3
Pd(PPh3)4
(a)ꢀ
(b)ꢀ
S
S
S
S
(29%)
toluene, 120 °C
5
6
Scheme 1. Synthesis of 3
The solid-state structure was unambiguously determined
by single crystal X-ray diffraction analysis (Figure 2a). The
quadrilateral porous structure was obtained. The crystal was
solved in the tetragonal space group I4/a. Therefore, only a
quarter unit is unique moiety. Molecules of 3 adopt a puckered
quadrilateral geometry with S4 symmetry (Figure 2b), and there
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Figure 3. a) Crystal void channel of 3, along the c-axis, and b) along the b-
axis.
To examine the potential ability of 3 as a receptor molecule,
complexation studies with C60 in solution was carried out.[18]
However, conventional titration experiments to determined
association constant in solution were unsuccessful, because
extremely insoluble materials appeared when a solution of C60
was added into a solution of 3. On the other hand, very slow
mixing of triple layer, composed of 3 in o-xylene, C60 in CS2, and
1,4-dioxane as a medium layer, gave black crystals suitable for
X-ray diffraction analysis.
Calix[4]arenes are know to have four conformers: 1,3-
alternate, 1,2-alternate, cone, and partial cone. However,
present selenacalxi[4]DTT has only limited conformers because
of the large TMS groups at the β position. From density
functional theory (DFT) calculations of 3, at B3LYP/6-31G(d,p)
level, 1,3-aleternate geometries with S4 (0.00 kJmol–1) and D2d
(+0.49 kJmol–1) are obtained as stable conformers (Table S2).[17]
The former, the most stable geometry, was a similar geometry
found in the crystal structure, and it adopts a puckered to avoid
steric hindrance of the TMS group. As shown in Figure 4, the
HOMO exhibits large amplitudes both on the Se atoms and DTT
skeleton. The lobes on the Se atoms and DTT units orthogonally
interact each other. In contrast, the LUMO mainly located on
DTT with quinoidal orbital topology.
(a)ꢀ
(b)ꢀ
c
b
(a)ꢀ
(b)ꢀ
b
a
Figure 5. (a) and (b) Molecular structure of 1:2 complex of 3•2C60 obtained by
X-ray analysis. Two C60 molecules are identical, although they are found as
statically disordered in the crytal. Blue lines indicate van der Waals contacts
between 3 and C60
.
The X-ray analysis of the solid-state structure revealed 1:2
composites of 3 and C60, together with residual solvent (xylene),
similar to those found in the complex of 2 with C60. The complex
crystalizes in the tetragonal system, I-4 space group. Both two
C60 molecules are crystallographically identical and exhibit static
disorder. The diagonally located two Se atoms are separated by
14.1 Å, and the size of the host molecule is larger than 2–C60
complex (diagonal distance of S•••S: 13.7Å). There are several
van der Waals, π-π and sulfur–π interactions between DTT units
of 3 and C60. In the crystal packing, the complex of 3•2C60
afforded highly symmetrical array along the axis direction.
Hence, C60 were closely packed in the crystal.
To gain further insight into the 1:2 complex formation, the
single point energy calculation were carried out at M05-2X/6-
31G(d,p) level. The molecular coordinates, extracted from the
geometries obtained by X-ray analysis, were employed for the
calculation of the complex. In the Kohn-Sham orbital plots, the
HOMO mainly locates on 3, while the LUMO are only found in
C60 molecules (Figure S5). The LUMO spread parallel to the
nearest two DTT units. The sum of the Mulliken charges on each
C60 molecule was small positive at +0.099 rather than negative,
while those on 3 was negative at –0.198 rather than positive.
Thus, the calculations demonstrate that no obvious electrostatic
interactions between one C60 and 3 in the ground state. In fact,
Raman spectroscopy does not exhibit detectable change
between 3•2C60 and free-C60. Therefore, charge-transfer
interactions would be a barely detectable level, if present that in
the crystal. Instead, van der Waals contacts between C60 and
two pair of DTT rings are contributed to form the complex in the
solid state.
Figure 4. Kohn-Sham plots of the (a) HOMO and (b) LUMO of 3.
Redox behavior of
3
was investigated by cyclic
voltammetry (CV) and differential pulse voltammetry (DPV) in a
1,2-dichloroethane solution. CV of 3 revealed reversible peaks
together with additional wave in higher potentials. Thus, we
recorded oxidation potential from DPV experiments that reveal
fine peaks. Table 1 summarized the oxidation potential obtained
ox
from DPV measurements. The first oxidation potential of 3 (E1
ox
ox
= +0.51 V vs. Fc/Fc+) is comparable to E1 and E2 of 2, which
are two one-electron oxidation processes, but it is much lower
than 4, which is a pristine DTT framework. Thus, the first redox
was owing to π-conjugated selenide of Se-DTT-Se moieties. It
suggests that the selenide linkers considerably enhance the
electron-donating ability of the DTT subunits. This result is
consistent with the electron density distribution of HOMO found
in DFT calculations.
Table 2. Oxidation potentials of 3 and related compounds. [a]
Compound
E1
E2
E3
ox
ox
ox
3
0.51
0.90
1.00
–
–
–
4 [b]
2 [c]
0.46 (1e–)
0.54 (1e–)
1.00
[a]
Obtained by DPV measurements in C2H4Cl2 containing 0.1
M
nBu4NPF6 at 25 °C with Pt working and counter electrodes. Potentials (V) were
measured against Ag/Ag+ using a luggin capillary and converted to the values
vs. Fc/Fc+. [b] CH2Cl2 was used as a solvent. [c]Data from ref. 6.
In conclusion, we have synthesized a novel Se-containing
macrocycle: selenacalix[4]dithienothiophene (selenacalix[4]DTT)
3, which is a cyclic tetramer of DTT linked with divalenent Se
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Eur. J. 2014, 20, 15298–15302; d) W. Gao, J. Wang, Q. Luo, Y. Lin, Y.
Ma, J. Dou, H. Tan, C.-Q. Ma, Z. Cui, RSC Adv. 2017, 7, 1606–1616.
a) B. König, M. Rödel, I. Dix, P. G. J. Jones, Chem. Res., Synop. 1997,
69;; b) J. Nakayama, N. Katano, Y. Sugihara, A. Ishii, Chem. Lett. 1997,
897; c) N. Katano, Y. Sugihara, A. Ishii, J. Nakayama, Bull. Chem. Soc.
Jpn. 1998, 71, 2695–2700.
atoms, via one-pot Pd-catalyzed reaction. A facile coupling of
dibromo DTT derivatives with (nBu3Sn)2Se gave 3 in moderate
yield. X-ray diffraction analysis revealed the molecular structure
having non-planar quadrilateral shape with S4 symmetry, and its
cavity arranged in channel-like columnar structure along the axis
direction thanks to the Se•••π intermolecular interactions. The
complex with two C60 was formed in the solid state via van der
Waals interactions, and it gives symmetrical three-dimensional
array of C60.
[5]
[6]
[7]
[8]
[9]
R. Inoue, M. Hasegawa, T. Nishinaga, K. Yoza, Y. Mazaki, Angew.
Chem. Int. Ed., 2015, 54, 2734–2738; Angew. Chem. 2015, 127, 2772–
2776.
a) M. Hasegawa, R. Inoue, Y. Mazaki, Synlett, 2016, 27, 2407–2415; b)
M. Hasegawa, Y. Honda, R. Inoue, Y. Mazaki, Chem. Asian J. 2016, 11,
674–677.
a) M. Kosugi, K. Shimizu, A. Ohtani, T. Migita, Chem. Lett. 1981, 829–
830; b) M. Kosugi, T. Ogata, M. Terada, H. Sano, T. Migita, Bull. Chem.
Soc. Jpn. 1985, 58, 3657–3658.
Acknowledgements
a) C. W. Nogueira, G. Zeni, J. B. T. Rocha, Chem. Rev. 2004, 104,
6255–6286; (b) S. T. Manjare,Y. Kim, Y.; D. G. Churchill, Acc. Chem.
Res. 2014, 47, 2985–2998.
This work was supported by JSPS KAKENHI (grant nos.
20438120 and 16K17871) and research grant from Kitasato
Research Center for Environment Science. The authors would
like to thank Dr. Masahumi Ueda, Dr. Yasutoshi Kasahara
(Kitasato University), Prof. Dr. Tohru Nishinaga (Tokyo
Metropolitan University), and Dr. Hiroyasu Sato (Rigaku Co.
Ltd.) for their helpful discussion. All calculations were performed
at the Research Center for Computational Science, Okazaki
(Japan).
[10] a) D. Jerome; A. Mazaud, M. Ribault, K. Bechugaard, Phys. Lett., 1980,
41, 95–98; b) T. Izawa, E. Miyazaki,K. Takimiya, Chem. Mater. 2009,
21, 903–912; c) M. Nakano, K. Niimi, E. Miyazaki, I. Osaka, K.
Takimiya, J. Org. Chem. 2012, 77, 8099–8111.
[11] S. Tashiro, M. Shionoya, Bull. Chem. Soc. Jpn. 2014, 87, 643–654.
[12] a) P. Kumar, V. S. Kashid, J. T. Mague, M. S. Balakrishna, Tetrahedron
Lett. 2014, 55, 5232–5235; b) J. Thomas, W. Maes, K. Robeyns, M.
Ovaere, L. V. Meervelt, M. Smet, W. Dehaen, Org. Lett. 2009, 11,
3040–3043; c) R. H. Mitchell, Tetrahedron Lett. 1975, 16, 1363–1364.
[13] H. Maeda, M. Takashima, K. Sakata, T. Watanabe, M. Honda, M. Segi,
Tetrahedron Lett. 2011, 52, 415–417.
Keywords: calix[n]arene • selenium •coupling reaction • C60
[14] Y. Nishiyama, K. Tokunaga, N. Sonoda, Org. Lett. 1999, 1, 1725–1727.
[15] F. E. Goodson, T. I. Wallow, B. M. Novak, J. Am. Chem. Soc. 1997,
119, 12441–12453.
complex • large void space
[1]
a) M. Iyoda, H. Shimizu, Chem. Soc. Rev. 2015, 44, 6411–6424; b) M.
E. Cinar, T. Ozturk, Chem. Rev. 2015, 115, 3036–3140; c) L. Zhang, N.
S. Colella, B. P. Cherniawski, S. C. B. Mannsfeld, A. L. Briseno, ACS
Appl. Mater. Interfaces, 2014, 6, 5327–5343; d) A. Mishra, C.-Q. Ma, P.
Bäuerle, Chem. Rev. 2009, 109, 1141–1276.
[16] J. Frey, A. D. Bond, A. B. Holmes, Chem. Commun. 2002, 2424–2425.
[17] Gaussian 16, Revision B.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel,
G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J.
Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V.
Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F.
Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D.
Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang,
M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A.
Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E.
N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J.
Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J.
Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W.
Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and
D. J. Fox, Gaussian, Inc., Wallingford CT, 2016.
[2]
[3]
I. F. Perepichka, D. F. Perepichka Eds., Handbook of Thiophene-based
Materials: Applications in Organic Electronics and Photonics, Wiley-
VCH: Chichester, U.K., 2009.
For selected examples, see: a) M. Iyoda, K. Tanaka, H. Shimizu, M.
Hasegawa, T. Nishinaga, T. Nishiuchi, Y. Kunugi, T. Ishida, H. Otani, H.
Sato, K. Inukai, K. Tahara, Y. Tobe, J. Am. Chem. Soc. 2014, 136,
2389–2396; b) F. Zhang, G. Götz, E. Mena-Osteritz, M. Weil, B. Sarkar,
W. Kaim, P. Bäuerle, Chem. Sci. 2011, 2, 781–784; c) T. Takahashi,
K.-i. Matsuoka, K. Takmiya, T. Otsubo, Y. Aso, J. Am. Chem. Soc.
2014, 127, 8928–8929; d) T. Nishinaga, S. Shiroma, M. Hasegawa, Org.
Lett. 2018, 20, 3426–3429.
[4]
For recent examples, see: a) M. Hasegawa, K. Kobayakawa, H.
Matsuzawa, T. Nishinaga, T. Hirose, K. Sako, Y. Mazaki, Chem. Eur. J.
2017, 23, 3267–3271; b) H. Ito, Y. Mitamura, Y. Segawa, K. Itami,
Angew. Chem., Int. Ed. 2015, 54, 159–163; Angew. Chem. 2015, 127,
161–165; c) F. Sannicoló, P. R. Mussini, T. Benincori, R. Cirilli, S.
Abbate, S. Arnaboldi, S. Casolo, E. Castiglioni, G. Longhi, R.
Martinazzo, M. Panigati, M. Pappini, E. Q. Procopio, S. Rizzo, Chem.
[18] For recent examples of C60 complex with π-conjugated macrocycle,
see: a) Y. Yamamoto, E. Tsurumaki, K. Wakamatasu, S. Toyota,
Angew. Chem. Int. Ed., 2018, 57, 8199–8202; b) H. Shimizu, C. J. Jose,
M. Hasegawa, T. Nishinaga,T. Haque, M. Takase, H. Otani, J. Rabe, M.
Iyoda, J. Am. Chem. Soc., 2015, 137, 3877–3885; c) K. Yoshida, A.
Osuka, Chem. Eur. J., 2016, 22, 9396–9403; d) E. Mena-Osteritz, P.
Bäuerle, Adv. Mater. 2006, 18, 447–451.
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Chemistry - An Asian Journal
COMMUNICATION
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COMMUNICATION
An efficient cyclization to
selena[4]calixdithienothiophene
has been developed. X-ray
analysis revealed there are
Masashi Hasegawa*, Kazuhiro
Takahashi, Ryota Inoue, Shiori Haga,
Yasuhiro Mazaki
Page No. – Page No.
intermolecular
interactions
Se••π
Selenacalix[4]dithienothiophene:
Synthesis, Structure, and
Complexation of A Cyclic Tetramer of
Selenide-Bridging Dithienothiophene
to
form
a
supramolecular
network,
leading to large void channel
space. Furthermore, the cyclic
compound forms 1:2 complex
with C60.
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