Tetraphenylethylene–Carborane–Tetraphenylethylene Triad: Influence of Steric Bridge on Aggregation-Induced Emission Properties

Article abstract of DOI:10.1002/asia.201801172

A novel tetraphenylethylene (TPE)–bridge–tetraphenylethylene triad has been synthesized, where the o-carboranyl moiety functions as a central bridge and two TPE units are in the lateral positions. This molecular triad has been characterized by various spectroscopic methods, and its structure has been studied by X-ray crystallography as well as theoretical calculations. The impact of the bridging carboranyl unit on the aggregation-induced emission (AIE) characteristics of the TPE–bridge–TPE triad has been investigated. When the central bridge is changed from one-dimensional (1D) alkynyl to three-dimensional (3D) carboranyl, the absolute luminescent quantum yield of the triad increased from 21.2 % to 54.7 % in the solid state, accompanied by a luminescence color change from blue to yellow (94 nm red-shift).

Full text of DOI:10.1002/asia.201801172

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Tetraphenylethylene−Carborane−Tetraphenylethylene Triad:
Influence of Steric Bridge on Aggregation-Induced Emission
Properties
Authors: Hong Yan, Yongheng Yin, Xiang Li, Senbo Yan, and
Changsheng Lu
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To be cited as: Chem. Asian J. 10.1002/asia.201801172
Link to VoR: http://dx.doi.org/10.1002/asia.201801172
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Tetraphenylethylene−Carborane−Tetraphenylethylene Triad:
Influence of Steric Bridge on Aggregation–Induced Emission
Properties
Yongheng Yin,a § Xiang Li,a § Senbo Yan,b Hong Yan,a * and Changsheng Lua,c *
Abstract:
A
novel
tetraphenylethylene
(TPE)-bridge-
conjugated systems with carborane derivatives, in order to
modulate their electronic, optical, and/or photophysical
functionalities.[10]
tetraphenylethylene triad has been synthesized, where the o-
carboranyl moiety functions as a central bridge and two TPE units
are in the lateral positions. This molecular triad has been
characterized by various spectroscopic methods, and its structure
has been studied by X-ray crystallography as well as theoretical
calculations. The impact of the bridging carboranyl unit on the
aggregation-induced emission (AIE) characteristics of the TPE-
bridge-TPE triad has been investigated. If the central bridge is
changed from one-dimensional (1D) alkynyl to three-dimensional
(3D) carboranyl, the absolute luminescent quantum yield of the triad
can be manipulated from 21.2% to 54.7% in the solid state,
accompanied by the luminescence color change from blue to yellow
(94 nm red shift).
In recent years, compounds that show fluorescence
enhancement in the solid state have attracted significant
interest.[11] TPEs are archetypal AIE-active luminogens, which
have been extensively studied and utilized in bio-probes[12]
,
chemical sensing[13], and optoelectronic systems[14]. Our group
and a couple of other groups have introduced TPE to the o-
carborane cage to yield novel AIE-active systems.[15] The
examples of carborane-functionalized TPE hybrids might shed
light on unique photophysical properties owing to the intrinsic
electronic feature and bulkiness of carboranyl units.
In this paper, we moved forward to study whether the three-
dimensional o–carboranyl cage could be a steric tool to tune the
luminescence of TPE-bridge-TPE triads, and in what way could
these ternary hybrids display AIE features.Therefore, the TPE-
carborane-TPE triad (3) has been synthesized for the first time
(Scheme S1). Our experimental data revealed that through the
change of the bridging linker from linear alkynyl to 3D steric o-
carboranyl (Scheme 1), the absolute luminescent quantum yield
of TPE-bridge-TPE triads can be significantly improved from
21.2% to 54.7% in solid state. Accordingly, the emission color
exhibits an evident shift from blue to yellow. Besides, density
functional theory (DFT) and time dependent DFT (TD–DFT)
calculations have been applied to investigate the ground-state
electronic structures of these TPE-bridge-TPE triads.
Solid-state emissive organic compounds with high
fluorescence quantum yields are promising materials due to their
potential applications in opto-electronic devices[1] and film-type
chemical sensors[2]. However, many conventional fluorophores
suffer from aggregation-caused quenching (ACQ) in the
condensed or solid state. Since the ACQ effect is unfavoured for
practical applications, many research groups have made
considerable efforts to solve this problem.[3] In 2001, Tang and
co-workers observed an extraordinary phenomenon that
silacyclopentadiene was non-luminescent in solution, but
remarkably emitted in the aggregate state, which was defined as
aggregation induced emission (AIE).[4] Now AIE is one of the
best solutions to ACQ, and has currently received intensive
attention owing to practical applications in materials science and
biological fields.[5]
o-Carborane is an icosahedral boron cluster with a three-
dimensional quasi-aromatic structure of the electrons, which
exhibits unique properties, such as highly polarizable σ-aromatic
character, highly thermal and chemical stability, and special
photophysical and electronic properties.[6,7] These have led to
very useful applications in biomedicine, materials, and so on.[8]
One of the more recent uses of carborane derivatives is the
construction of luminescent materials.[9] In the past decade,
several groups have focused on combination of organic π-
Scheme 1. Structures of the ternary TPE derivatives 1–3.
Compounds
1 and 2 were synthesized according to
literature procedures.[16] TPE-carborane-TPE (3) was prepared
by the reaction of B10H12(Et2S)2 and compound 1 under
refluxing condition in moderate yield (see Supporting
Information ). The new product was characterized by NMR, IR,
and mass spectroscopies (Figures S1-S5), which shows
excellent stability toward air and light under ambient conditions
and excellent solubility in common organic solvents such as
CHCl3, CH2Cl2, THF and toluene.
[a]
Y. Yin, Dr. X. Li, Prof. Dr. H. Yan and Prof. Dr. C. Lu
State Key Laboratory of Coordination Chemistry, Jiangsu Key
Laboratory of Advanced Organic Materials, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing 210023, China.
E-mail: hyan1965@nju.edu.cn, luchsh@nju.edu.cn
Senbo Yan
College of Mechanics and Materials, Hohai University, Nanjing
210000, China
Prof. Dr. C. Lu
National Demonstration Center for Experimental Chemistry
Education, Nanjing University, Nanjing 210023, China
The financial support from the National Natural Science Foundation
of China (21531004 and 21472086), and high-performance
computational center of Nanjing University.
[b]
[c]
The structure of
3 was further confirmed by X-ray
crystallographic analysis (Figure 1 and Table S1). In 3, the four
phenyl groups in the TPE unit adopt a propeller arrangement
around the central C=C bond, similar to previously reported
[**]
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TPE-based molecules.[17] It is noted that the C=C bond length in
the TPE cores has been shortened to 1.347 Å owing to the
introduction of carborane, in comparison to 1.359 Å in free TPE.
The shrinkage of the central C=C bond making it the most rigid
structure, indicating that two vicinal ethylene bridges (–CH2–
CH2–) do effectively restrict the motion of the C-C bond, which
suggesting that the presence of carboranyl group might be
conducive to the restrained intramolecular rotation (RIR) effect.
The C1-C2 bond length in 3 is 1.727 Å. In the packing diagram
(Figure S8), 3 displays a slipped stacking alignment with parallel
carborane cages in each stacking column. No distinct π–π
stacking interaction is found owing to the lack of planarity of the
molecular skeleton with respect to the twisted conformation in
each triad. Obviously, the three-dimensional carborane bridge in
the central triad has remarkably altered both the molecular
structure and the packing model in solid state. Owing to the
relatively compact packing style in crystal, compound 3 seems
to be able to have higher luminescence quantum yield.
vibrational structures. All the compounds exhibit broad
featureless absorption bands in the ultraviolet region, which are
typically originated from π–π* transitions of the aromatic
skeletons. The absorption onset of 3 (321 nm) is blue-shifted in
comparison to 1 (348 nm) and 2 (340 nm), and its molar
absorption is decreased. The optical bandgaps were calculated
to be 2.93 eV, 3.00 eV and 3.05 eV, respectively, indicating that
3 possesses a wider transition gap. Clearly, the bridging group
has played a more pronounced role in the absorption intensity in
the case of carborane-containing triad.
500
1
2
3
400
300
200
100
0
0
20
40
60
80
100
Water fraction (vol%)
Figure 3. Plot of emission intensity of 1, 2 and 3 versus the composition of the
aqueous mixture
Photoluminescence (PL) spectra were recorded in THF
(Figure S9). As expected, all the compounds display very weak
fluorescence emission, which should be subjected to non-
radiative processes arising from the rotation of TPE units.
Compound 3 shows fluorescence maximum at 558 nm, 100 nm
red shift in sharp contrast to compounds 1 and 2.
To determine the AIE effects of TPE-bridge-TPE triads in
aggregate state, the emission spectra in the binary THF–H2O
solution with different volumetric ratios (fw, vol%) of water were
recorded, and shown in Figures 3 and 4. Compound 3 virtually
shows weak emission in THF, which is a typical behavior of TPE-
cored luminophore. If the fraction of water in the THF–water
mixture is kept at the levels less than 80%, the PL emission
remains weak and little varied. However, if fw is reached to 80%,
a bright orange red emission band emerges at 563 nm. The
water content of 99% swiftly enhances the emission intensity
with a blue shift (16 nm) from 563 nm to 547 nm owing to the
molecular aggregation that leads to strong yellow emission. The
emission intensity is remarkably increased by 524-fold
compared with that in pure THF solution (Figure 4), indicating
that the aggregation-driven growth is the main reason for the
observed emission enhancement.[20] Note that with low levels of
water content the fluorescence spectra of compound 3 display a
flat line approximately parallel to the baseline, manifesting poor
fluorescence behavior. But the later formation of aggregates
inhibits the intramolecular rotation processes, thus populates the
radiative decay channel of the excitation, as a result, the
fluorescence is strongly enhanced. It is noted that in the cases
of compounds 1 and 2, the fluorescence intensity reaches the
maximum at a fraction of water of 95% (v/v), but is slightly
decreased at a higher fraction of water, indicative the AIE
molecules have formed particles in high water fraction.
Figure 1． Single-crystal structure of compound 3 with thermal ellipsoids
drawn at the 30% probability level. H atoms are omitted for clarity.
5
4
3
1
2
3
2
1
0
250 275 300 325 350 375 400
Wavelength (nm)
Figure 2. Absorption spectra of compounds 1, 2, and 3 in THF (1.0 × 10–6 M)
at room temperature.
TPE and its derivatives are known to have exceedingly short
singlet excited-state lifetimes, negligible fluorescence quantum
yields in solution and slow rates of intersystem crossing.[18]
Herein, we have explored the emission/optical behavior of TPE
moieties after if incorporated into various triads. The UV-vis
absorption spectra were recorded in THF (Figure 2) which show
similar profiles as that of free TPE[19] with poorly resolved
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Figure 4. (a) Emission spectra of 1, 2, and 3 in THF, upon increasing water from 0% to 99% (λex = 340 nm); (b) Photograph of 1, 2, and 3 in THF/H2O solution
with various fractions of water (fw) taken under UV light (365 nm). Solution concentration: 10–5 M.
The fluorescence quantum yields are observed to be in the
sequence of 1 (21.2%) < 2 (28.8%) < 3 (54.7%) in powder solid
state. In addition, fluorescence lifetimes of these luminogens are
in accordance with the tendency of the fluorescence quantum
yields (Table S2). On the basis of the values of ΦPL and τ, we
can obtain the radiative rate constant (kf) and non-radiative rate
constant (knf) (Table S2): kf = ΦPL/τ; knf = kf(1-ΦPL)/ΦPL, where
ΦPL is the fluorescence quantum yield and τ is the fluorescence
lifetime. For compound 3, the radiative rate constant (kf) is close
to the non-radiative rate constant (knf), thus displaying high
quantum yields. However, the radiative rate constant (kf) is much
less than the non-radiative ones (knf) in the cases of 1 and 2,
where the non-radiative transition plays a crucial role in the
decay of excited states. In aggregates, free rotation of the
phenyl groups in TPE units are more suppressed in the case of
3, thus the corresponding non-radiative decay is decreased.
HOMOs and LUMOs are distributed over the whole molecules in
the cases of 1 and 2. However, in 3 the LUMO is occupied by
the whole molecule, whereas the HOMO is concentrated on one
of the TPE groups. The conjugation between TPE and
carborane moiety in 3 is reduced due to the spacial repulsion,
which also leads to a larger energy gap between the decreased
LUMO and HOMO. This phenomenon is in agreement with the
spectral data.
Figure 6. Molecular orbitals of HOMO and LUMO levels of 1, 2, and 3,
calculated by using the B3LYP/6−31G(d,p) basis set.
1
1
2
3
Figure 5. Photographs of the compounds under a) sunlight, and b) 365 nm
light. The normalized FL spectra of 1, 2 and 3 in powder states at room
temperature (λex = 340 nm).
0.0
0.4
0.8
1.2
1.6
Potential (V)
In order to get an insight into the electronic structures of these
luminogens, theoretical calculations were performed based on
density functional theory (DFT). Geometries of the as-prepared
molecules were optimized at the B3LYP/6-31G(d,p) level, and
the frontier molecular orbitals are shown in Figure 6. The
Figure 7. Cyclic voltammograms of 1, 2 and 3 measured in dry CH2Cl2
(oxidation) with 0.1 M TBAPF6 as supporting electrolyte at a scan rate of 100
mV s–1
.
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R. Duan, Y. Xie, Y. Yi, Q. Peng, R. Hu, A. Qin, Z. Zhao and B. Z. Tang,
Angew. Chem. Int. Ed., 2015, 127, 14700-14705; (g) B. Dhokale, T.
Jadhav, S. M. Mobin and R. Misra, J. Org. Chem., 2015, 80, 8018-8025;
(h) Y. Yuan, S. Xu, X. Cheng, X. Cai and B. Liu, Angew. Chem. Int. Ed.,
2016, 55, 6457-6461; (i) C.-J. Zhang, G. Feng, S. Xu, Z. Zhu, X. Lu, J.
Wu and B. Liu, Angew. Chem. Int. Ed., 2016, 55, 6192-6196.
Cyclic voltammetry (CV) was employed to evaluate the
HOMO/LUMO levels, and the tested potentials were listed in
Table S3. The CV data are in good agreement with the results
obtained from theoretical calculations.
In summary, we have developed a novel TPE-carborane-TPE
triad and investigated the role of carboranyl linker in the AIE
characteristics of the TPE-bridge-TPE triad. Our results herein
imply that if the linking bridge is altered from alkynyl to
carboranyl, the luminescent quantum yield of the TPE-bridge-
TPE triad can be significantly increased from 21.2% to 54.7% in
solid state and the emission color exhibits an obvious 94 nm red
shift (from blue to yellow).
[6]
[7]
(a) R. N. Grimes, in Carboranes (Third Edition), Academic Press,
Boston, 2016; (b) J. Poater, M. Solà, C. Viñas, F. Teixidor, Angew.
Chem. 2014, 126, 12387-12391.
(a) J. J. Peterson, A. R. Davis, M. Werre, E. B. Coughlin, K. R. Carter,
ACS App. Mater. Inter., 2011, 3, 1796-1799; (b) J. Cabrera-González,
V. Sánchez-Arderiu, C. Viñas, T. Parella, F. Teixidor, R. Núñez, Inorg.
Chem., 2016, 55, 11630-11634; (c) J. Cabrera‐González, L. Cabana, B.
Ballesteros, G. Tobias, R. Núñez, Chem. Eur. J, 2016, 22, 5096-5101;
(d) S. Qi, H. Wang, G. Han, Z. Yang, A. Zhang Xiao, S. Jiang, Y. Lu, J.
App. Poly. Sci., 2016, 133.
[8]
(a) J. F. Valliant, K. J. Guenther, A. S. King, P. Morel, P. Schaffer, O. O.
Sogbein, K. A. Stephenson, Coord. Chem. Rev., 2002, 232, 173-230;
(b) B. Sivaev Igor, V. Bregadze Vladimir, Eur. J. Inorg. Chem., 2009,
2009, 1433-1450; (c) F. Issa, M. Kassiou, L. M. Rendina, Chem.
Rev.,2011, 111, 5701-5722; (d) M. Scholz, E. Hey-Hawkins, Chem.
Rev., 2011, 111, 7035-7062; (e) B. P. Dash, R. Satapathy, J. A.
Maguire, N. S. Hosmane, N. J. Chem., 2011, 35, 1955-1972; (f) J. J.
Schwartz, A. M. Mendoza, N. Wattanatorn, Y. Zhao, V. T. Nguyen, A. M.
Spokoyny, C. A. Mirkin, T. Baše, P. S. Weiss, J. Am. Chem. Soc, 2016,
138, 5957-5967; (g) R. Nunez, I. Romero, F. Teixidor, C. Vinas,
Chem.Soc. Rev., 2016, 45, 5147-5173.
Acknowledgements
Yongheng Yin and Dr. Xiang Li contributed equally to this
work. This work was supported by the National Natural Science
Foundation of China (21472086 and 21531004), and the high-
performance computational center of Nanjing University.
Conflict of interest
[9]
(a) T. Kim, H. Kim, K. M. Lee, Y. S. Lee, M. H. Lee, Inorg. Chem., 2013,
52, 160-168; (b) C. Shi, H. Sun, Q. Jiang, Q. Zhao, J. Wang, W. Huang,
H. Yan, Chem. Commun., 2013, 49, 4746-4748; (c) K. C. Song, H. Kim,
K. M. Lee, Y. S. Lee, Y. Do, M. H. Lee, Dalton. Trans., 2013, 42, 2351-
2354; (d) A. M. Prokhorov, T. Hofbeck, R. Czerwieniec, A. F.
Suleymanova, D. N. Kozhevnikov, H. Yersin, J. Am. Chem. Soc.,2014,
136, 9637-9642; (e) T. Kim, J. Lee, S. U. Lee, M. H. Lee,
Organometallics 2015, 34, 3455-3458; (f) K. O. Kirlikovali, J. C. Axtell,
A. Gonzalez, A. C. Phung, S. I. Khan, A. M. Spokoyny, Chem. Sci.,
2016, 7, 5132-5138; (g) S. Mukherjee, P. Thilagar, Chem. Commun.,
2016, 52, 1070-1093; (h) R. Núñez, M. Tarrés, A. Ferrer-Ugalde, F. F.
de Biani, F. Teixidor, Chem. Rev., 2016, 116, 14307-14378.
The authors declare no conflict of interest.
Keywords: carboranes • tetraphenylethylene (TPE) • emission •
aggregation-induced emission (AIE) • photophysical properties
[1]
(a) R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N.
Marks, C. Taliani, D. D. C. Bradley, D. A. D. Santos, J. L. Brédas, M.
Lögdlund, W. R. Salaneck, Nature 1999, 397, 121; (b) F. Cicoira, C.
Santato, Adv. Funct. Mater. 2007, 17, 3421-3434; (c) J. Zaumseil, H.
Sirringhaus, Chem. Rev. 2007, 107, 1296-1323; (d) R. Yeh-Yung Lin,
H.-W. Lin, Y.-S. Yen, C.-H. Chang, H.-H. Chou, P.-W. Chen, C.-Y. Hsu,
Y.-C. Chen, J. T. Lin, K.-C. Ho, Energy & Environmental Science 2013,
6, 2477-2486; (e) K. O. Kirlikovali, J. C. Axtell, A. Gonzalez, A. C.
Phung, S. I. Khan, A. M. Spokoyny, Chem. Sci. 2016, 7, 5132-5138; (f)
C. Wang, Z. Liu, M. Li, Y. Xie, B. Li, S. Wang, S. Xue, Q. Peng, B.
Chen, Z. Zhao, Q. Li, Z. Ge, Z. Li, Chem. Sci. 2017, 8, 3750-3758.
(a) Y. Liu, Y. Tang, N. N. Barashkov, I. S. Irgibaeva, J. W. Y. Lam, R.
Hu, D. Birimzhanova, Y. Yu, B. Z. Tang, J. Am. Chem. Soc.,2010, 132,
13951-13953. (b) Y. Liu, C. Deng, L. Tang, A. Qin, R. Hu, J. Z. Sun, B.
Z. Tang, J. Am. Chem. Soc., 2011, 133, 660-663; (c) D. Ding, K. Li, B.
Liu, B. Z. Tang, Acc. Chem. Res., 2013, 46, 2441-2453; (d) R. Yoshii, A.
Hirose, K. Tanaka, Y. Chujo, J. Am. Chem. Soc., 2014, 136, 18131-
18139. (e) T. Beppu, K. Tomiguchi, A. Masuhara, Y. J. Pu, H. Katagiri,
Angew. Chem. Int. Ed., 2015, 54, 7332-7335; (f) O. Ostroverkhova,
Chem. Rev. 2016, 116, 13279-13412.
[10] (a) B. P. Dash, R. Satapathy, E. R. Gaillard, K. M. Norton, J. A. Maguire,
N. Chug, N. S. Hosmane, Inorg. Chem., 2011, 50, 5485-5493; (b) K. R.
Wee, Y. J. Cho, K. Song Jae, O. Kang Sang, Angew. Chem. Int. Ed.,
2013, 52, 9682-9685; (c) L. Weber, J. Kahlert, R. Brockhinke, L.
Bohling, J. Halama, A. Brockhinke, H.-G. Stammler, B. Neumann, C.
Nervi, R. A. Harder, M. A. Fox, Dalton Trans. 2013, 42, 10982-10996;
(d) H. J. Bae, H. Kim, K. M. Lee, T. Kim, Y. S. Lee, Y. Do, M. H. Lee,
Dalton. Trans. 2014, 43, 4978-4985; (e) M. Tominaga, H. Naito, Y.
Morisaki, Y. Chujo, N. J. Chem ., 2014, 38, 5686-5690; (f) J. Guo, D.
Liu, J. Zhang, J. Zhang, Q. Miao, Z. Xie, Chem. Commun., 2015, 51,
12004-12007; (g) S.-Y. Kim, A.-R. Lee, G. F. Jin, Y.-J. Cho, H.-J. Son,
W.-S. Han, S. O. Kang, J. Org. Chem., 2015, 80, 4573-4580; (h) D. Tu,
P. Leong, Z. Li, R. Hu, C. Shi, K. Y. Zhang, H. Yan, Q. Zhao, Chem.
Commun., 2016, 52, 12494-12497; (i) J. Park, Y. H. Lee, J. Y. Ryu, J.
Lee, M. H. Lee, Dalton Trans., 2016, 45, 5667-5675; (j) H. Naito, K.
Nishino, Y. Morisaki, K. Tanaka, Y. Chujo, Angew. Chem. Int. Ed., 2016,
56, 254-259.
[2]
[3]
[4]
[5]
(a) Y. Hong, J. W. Y. Lam and B. Z. Tang, Chem. Soc. Rev., 2011, 40,
5361-5388; (b) J. Mei, N. L. C. Leung, R. T. K. Kwok, J. W. Y. Lam and
B. Z. Tang, Chem. Rev, 2015, 115, 11718-11940.
[11] (a) M. Shimizu, T. Hiyama, Chem. Asian. J., 2010, 5, 1516-1531; (b) P.
Anthony Savarimuthu, ChemPlusChem 2012, 77, 518-531; (c) J.
Gierschner, S. Y. Park, J. Mater. Chem. C 2013, 1, 5818-5832; (d) S.
Mukherjee, P. Thilagar, Proc.Natl. Acad. Sci., India Section A: Phys.
Sci., 2014, 84, 131-149; (e) Q. Li, Z. Li, Adv. Sci., 2017, 4, 1600484.
[12] (a) C. W. T. Leung, Y. Hong, S. Chen, E. Zhao, J. W. Y. Lam and B. Z.
Tang, J. Am. Chem. Soc., 2013, 135, 62-65; (b) S. Li, Y. Shang, E.
Zhao, R. T. K. Kwok, J. W. Y. Lam, Y. Song and B. Z. Tang, J.
Mater.Chem. C, 2015, 3, 3445-3451. (c) B. Situ, S. Chen, E. Zhao, C.
W. T. Leung, Y. Chen, Y. Hong, J. W. Y. Lam, Z. Wen, W. Liu, W.
Zhang, L. Zheng and B. Z. Tang, Adv. Funct. Mater., 2016, 26, 7132-
7138.
J. D. Luo, Z. L. Xie, J. W. Y. Lam, L. Cheng, H. Y. Chen, C. F. Qiu, H. S.
Kwok, X. W. Zhan, Y. Q. Liu, D. B. Zhu and B. Z. Tang, Chem.
Commun., 2001, 1740-1741.
(a) W. Z. Yuan, F. Mahtab, Y. Gong, Z.-Q. Yu, P. Lu, Y. Tang, J. W. Y.
Lam, C. Zhu and B. Z. Tang, J. Mater. Chem., 2012, 22, 10472-10479;
(b) J. Wang, J. Mei, R. Hu, J. Z. Sun, A. Qin and B. Z. Tang, J. Am.
Chem. Soc., 2012, 134, 9956-9966; (c) C. Y. K. Chan, Z. Zhao, J. W. Y.
Lam, J. Liu, S. Chen, P. Lu, F. Mahtab, X. Chen, H. H. Y. Sung, H. S.
Kwok, Y. Ma, I. D. Williams, K. S. Wong and B. Z. Tang, Adv. Funct.
Mater., 2012, 22, 378-389; (d) J. Zhou, Z. Chang, Y. Jiang, B. He, M.
Du, P. Lu, Y. Hong, H. S. Kwok, A. Qin, H. Qiu, Z. Zhao and B. Z. Tang,
Chem. Commun., 2013, 49, 2491-2493; (e) R. Hu, J. W. Y. Lam, Y. Liu,
X. Zhang and B. Z. Tang, Chem. Eur. J, 2013, 19, 5617-5624; (f) F. Bu,
[13] (a) K. R. Ghosh, S. K. Saha, J. P. Gao and Z. Y. Wang, Chem.
Commun., 2014, 50, 716-718. (b) Y. Yuan, C.-J. Zhang, R. T. K. Kwok,
S. Xu, R. Zhang, J. Wu, B. Z. Tang and B. Liu, Adv. Funct. Mater., 2015,
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25, 6586-6595; (c) X. Gao, G. Feng, P. N. Manghnani, F. Hu, N. Jiang,
J. Liu, B. Liu, J. Z. Sun and B. Z. Tang, Chem. Commun., 2017, 53,
1653-1656.
[14] (a) W. Z. Yuan, P. Lu, S. Chen, J. W. Y. Lam, Z. Wang, Y. Liu, H. S.
Kwok, Y. Ma and B. Z. Tang, Adv. Mater., 2010, 22, 2159-2163; (b) Z.
Zhao, S. Chen, X. Shen, F. Mahtab, Y. Yu, P. Lu, J. W. Y. Lam, H. S.
Kwok and B. Z. Tang, Chem. Commun., 2010, 46, 686-688; (c) W. Z.
Yuan, S. Chen, J. W. Y. Lam, C. Deng, P. Lu, H. H. Y. Sung, I. D.
Williams, H. S. Kwok, Y. Zhang and B. Z. Tang, Chem. Commun., 2011,
47, 11216-11218; (d) Z. Zhao, J. W. Y. Lam and B. Z. Tang, J.
Mater.Chem., 2012, 22, 23726-23740. (e) C. Y. K. Chan, J. W. Y. Lam,
C. Deng, X. Chen, K. S. Wong and B. Z. Tang, Macromolecules, 2015,
48, 1038.
[15] (a) X. Li, Y. Yin, H. Yan, C. Lu, Chem. Asian. J., 2017, 12, 2207-2210;
(b) J. Cabrera ‐ González, S. Bhattacharyya, B. Milián ‐ Medina, F.
Teixidor, N. Farfán, R. Arcos‐Ramos, V. Vargas‐Reyes, J. Gierschner,
R. Núñez, Eur. J. Inorg. Chem., 2017, 2017, 4575-4580. (c) Y. Nie, H.
Zhang, J. Miao, X. Zhao, Y. Li, G. Sun, J. Organomet. Chem., 2018;
(d)J. Li, C. Yang, X. Peng, Y. Chen, Q. Qi, X. Luo, W.-Y. Lai, W. Huang,
J. Mater. Chem. C., 2018, 6, 19-28.
[16] (a) M. Banerjee, S. J. Emond, S. V. Lindeman, R. Rathore, J. Org.
Chem., 2007, 72, 8054-8061; (b) R. Hu, W. Y. Lam Jacky, Y. Liu, X.
Zhang, Z. Tang Ben, Chem. Eur. J., 2013, 19, 5617-5624.
[17] (a) B. Xu, Z. Chi, J. Zhang, X. Zhang, H. Li, X. Li, S. Liu, Y. Zhang, J.
Xu, Chem. Asian. J., 2011, 6, 1470-1478. (b) Z. Zhao, Z. Chang, B. He,
B. Chen, C. Deng, P. Lu, H. Qiu, Z. Tang Ben, Chem. Eur. J., 2013, 19,
11512-11517.
[18] (a) D. A. Shultz, M. A. Fox, J. Am. Chem. Soc.,1989, 111, 6311-6320;
(b) J. Ma, M. B. Zimmt, J. Am. Chem. Soc.,1992, 114, 9723-9724; (c) R.
Tang, X. Wang, W. Zhang, X. Zhuang, S. Bi, W. Zhang, F. Zhang, J.
Mater. Chem. C., 2016, 4, 7640-7648.
[19] R. Hu, N. L. C. Leung, B. Z. Tang, Chem. Soc. Rev., 2014, 43, 4494-
4562.
[20] (a) P. Galer, R. C. Korošec, M. Vidmar, B. Šket, J. Am. Chem.
Soc.,2014, 136, 7383-7394; (a) Z. Zhang, Y.-S. Wu, K.-C. Tang, C.-L.
Chen, J.-W. Ho, J. Su, H. Tian, P.-T. Chou, J. Am. Chem. Soc., 2015,
137, 8509-8520.
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10.1002/asia.201801172
Chemistry - An Asian Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Yongheng Yin, Xiang Li, Senbo Yan,
Hong Yan,* and Changsheng Lu*
In this paper, the impact of
carboranyl linker on the AIE
characteristics of TPE–
Page No. – Page No.
bridge-TPE
investigated
has
and
been
the
Tetraphenylethylene−Carborane−
Tetraphenylethylene Triad: Influence
of Steric Bridge on Aggregation–
Induced Emission Properties
luminescent quantum yield
can be tuned from 21.2% to
54.7% in solid state and red-
shift emission of 94 nm is
observed.
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