Crystal Multi-Conformational Control Through Deformable Carbon-Sulfur Bond for Singlet-Triplet Emissive Tuning

Article abstract of DOI:10.1002/anie.201900703

Crystal-state luminophores have been of great interest in optoelectronics for years, whereas the excited state regulation at the crystal level is still restricted by the lack of control ways. We report that the singlet-triplet emissive property can be pro

Full text of DOI:10.1002/anie.201900703

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Crystal Multi-Conformational Control Through Deformable
Carbon–Sulfur Bond for Singlet–Triplet Emissive Tuning
Authors: Hongwei Wu, Weijie Chi, Gleb Baryshnikov, Bin Wu, Yifan
Gong, Dongxiao Zheng, Xin Li, Yanli Zhao, Xiaogang Liu,
Hans Ågren, and Liangliang Zhu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201900703
Angew. Chem. 10.1002/ange.201900703
Link to VoR: http://dx.doi.org/10.1002/anie.201900703
http://dx.doi.org/10.1002/ange.201900703

10.1002/anie.201900703
Angewandte Chemie International Edition
COMMUNICATION
Crystal Multi-Conformational Control Through Deformable
Carbon–Sulfur Bond for Singlet–Triplet Emissive Tuning
Hongwei Wu+, Weijie Chi+, Gleb Baryshnikov, Bin Wu, Yifan Gong, Dongxiao Zheng, Xin Li, Yanli Zhao,
Xiaogang Liu, Hans Ågren, and Liangliang Zhu*
Abstract: Crystal-state luminophores have been of great interest in
optoelectronics for years, whereas the excited state regulation at the
crystal level is still restricted by the lack of control ways. We report
that the singlet–triplet emissive property can be profoundly regulated
by crystal conformational distortions. Employing fluoro-substituted
tetrakis(arylthio)benzene luminophores as prototype, we found that
couples of molecular conformations formed during different
crystallizations. The deformable carbon–sulphur bond essentially
drove the distortion of the molecular conformation and varied the
stacking mode, together with diverse non-covalent interactions,
leading to the proportional adjustment of the fluorescence and
phosphorescence bands. This intrinsic strategy was further applied
conformational deformability to control the emissive pathways at
the crystal level.
Since fluorescence and phosphorescence in a single system
generally cover individual spectral regions with a sizable energy
difference, the regulation of singlet–triplet emissive pathways
has raised significant concerns for advanced luminescent
materials. [29, 30] Here we present a strategy of imposing crystal
multi-conformational control for achieving the tunable dual
emission. The strategy is inspired by that molecular
conformation, not only molecular structure, can largely affect the
material photophysics including the intersystem crossing (ISC)
rates.[31-34] We are intended to introduce deformable covalent
bonds upon molecular crystallization to produce distortable
conformations with different stackings, for manufacturing a
material with fluorescent–phosphorescent proportion adjustable.
Multi-sulfurated aromatic compounds are prone to take effect
metal-free room-temperature phosphorescence emitters in
which the ISC process is environmentally adjustable.[35-38] The
compounds can be readily synthesized from low-cost precursors
with different functional groups modified for postprocessing.[39-41]
Herein, we designed and synthesized two fluoro-substituted
tetrakis(arylthio)benzene molecules (compound 1 and 2, Figure
1), based on the anticipation that the multiple C-S bond can be
deformable for tuning the molecular conformation with diverse
intermolecular non-covalent interaction (e.g. CH–F bond, CH–π,
S–S interaction, π–π stacking, etc.). Thus, the conformational
distortion and stack ability to different degree can be achieved
during different crystallizations, followed by a regulation of the
singlet–triplet emissive pathways.
The crystal growth of 1 and 2 can be affected by a variety of
applied solvent conditions. We here investigated six
representative single-crystal materials of 1, namely a DCM–IPR
one (from dichloromethane and isopropanol), an ETH–EA crystal
(prepared from ethanol and ethyl acetate), a TOL–BUT one (from
Toluene and Butanol), an ACN one (from acetonitrile), a THF–IPR
one (from Tetrahydrofuran and isopropanol) and an EA one (from
ethyl acetate). These crystals show distinct photoluminescence
properties (Figure 2a). The DCM-IPR and ETH–EA reveal a multi-
band emission spectrum with 420 nm signal dominance with a
blue luminescent color. The TOL-BUT, ACN and THF-IPR
crystals show even stronger emission band of 475–550 nm
relative to the 420 nm one, resulting in cyan to deeper cyan
luminescent colors. In the EA crystal, the emission band around
420 nm is extremely suppressed, and exhibits instead a higher
emission band of 450–560 nm with a green luminescent color.
The difference in luminescent color originates from the synergy of
these multi-band emission signals dominated by discrete
wavelengths. The CIE chromaticity diagram signifies the color
parameters of the corresponding crystals (Figure 2b). Meanwhile,
time-resolved emission measurements upheld the fluorescence or
phosphorescence components in the multi-band emission (Figure
2c, 2d , 2e, S11, and S12).
for
solid-state
multicolor
emissive
conversion
and
mechanoluminescence, probably offering new insights for design of
smart crystal luminescent materials.
Solid-state organic luminogens play a significant role in modern
optoelectronics, light-emitting materials, luminescent displays
and light sources.[1-11] In particular, luminogens that can work in
the crystal phase have generated a considerable interest due to
their material anisotropy, stability and the potential to construct
perfect optoelectronic devices with low defect density.[12-16] The
past years witnessed substantial progress in developing crystal-
state emissions, the study and application of which have been
principally focused on luminescent color tuning, brightness
adjustment and device fabrication.[17-22] Nevertheless, regulation
of emissive pathways (e.g. regarding singlet–triplet excited state
features or the transfer in between) on single materials by
crystal engineering has received little attention, probably
because such a excited state regulation often lacks sensitivity in
a crystalline system.[14] In contrast, it is known that emissive
pathways can basically respond to diverse structural and self-
assembly factors in amorphous phases.[23-28] This factor makes it
desirable to develop an intrinsic strategy of enrolling molecular
[*]
Dr. H. Wu, Mr. B. Wu, Mr. Y. Gong, Mr. D, Zheng, Prof. Dr. L. Zhu
State Key Laboratory of Molecular Engineering of Polymers
Department of Macromolecular Science
Fudan University, Shanghai 200438 china
E-mail: zhuliangliang@fudan.edu.cn
Dr. H. Wu, Prof. Y. Zhao
Division of Chemistry and Biological Chemistry, School of Physical
and Mathematical Sciences, Nanyang Technological University, 21
Nanyang Link, Singapore 637371.
Dr. W. Chi, Prof. X. Liu, Singapore University of Technology and
Design, 8 Somapah Road, 487372, Singapore
Dr. G. Baryshnikov, Dr. X. Li, Prof. Dr. H. Ågren
Division of Theoretical Chemistry and Biology
School of Biotechnology, KTH Royal Institute of Technology
SE-10691 Stockholm, Sweden
[+]
These authors contributed equally.
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201900703
Angewandte Chemie International Edition
COMMUNICATION
Figure 1. Illustration of the formation of various single-crystal structures of 1 and 2 under different crystal growth conditions. The deformable C-S bond with
diverse non-covalent interactions dominate the crystal polymorphism nature, and the multi-color labelling of these single-crystal structures represents the
corresponding luminescent color of fluorescence–phosphorescence emission, along with the multi-conformational change. The luminescence mechanism is linked
to the degree of the molecular conformational distortion, namely, higher tense conformations give rise to a fluorescence-dominant emission since ISC is
weakened by relatively restricted molecular vibrations, whereas the lower tense conformations are prone to produce phosphorescence-dominant emission when
lacking the restrictive factors and allowing for an effective ISC process.
It could be found that either conformational pairs in a triclinic
lattice (P 1) or a single conformation in a monoclinic lattice (P
21/c) can be formed during the crystallization of 1. The
covalent interactions in the singlet crystal system, confirmed by
the intermolecular short actions marked in Figure S16-S20,
namely, CH–F bond, CH–π, S–S interaction and π–π stack can
be seen in these conformations (Figure 3a-c) . After obtaining
the spin-orbit coupling (SOC) (ξ) change (Figure 3d) in different
crystal through computational simulation and the KISC change
from the experiments (Table S1),[43a] we found that the evaluated
SOC ξ (S1, T1; S0, T1) increased largely from DCM-IPR crystal
(1.198 eV; 0.957 eV) to TOU-BUT crystal (1.201 eV; 1.157 eV)
and to THF-IPR crystal (1.222 eV; 1.294 eV). That is to say, in
the more rigid crystals, strong intermolecular interactions
promote the ISC from singlet to triplet state and lead to the
higher ratio of phosphorescence at room temperature. This was
further clarified by an ISC rate increase from DCM-IPR crystal
(1.1 ×107 s−1) to TOU-BUT crystal (1.9 ×108 s−1) and to THF-IPR
crystal (4.1 × 108 s−1). Such an improvement in ISC may be due
to the stronger intermolecular interactions that can induce
stronger out-of-plane vibration to contribute to the spin orbit
coupling.[43b] The fluorescence and phosphorescence ratio
change is due to the deformability of the C-S-C bond, which
determined the molecular conformation and the crystal
environment assisted by a variety of intermolecular interactions.
Compared to those fluorescence dominant crystals (Figure 3a),
the intermolecular interactions in the phosphorescence-
dominant crystals (Figure 3b, 3c) enhanced the degree of
molecular confinement, thereby improving the SOC and
resulting in an increased ratio in phosphorescence.
conformational pairs include
a
symmetrical and an
unsymmetrical conformation. All of them are distinct as
monitored by the C-S-C bond angles in the crystal form (Figure
2f), which reflect the conformational change and significantly
affect the band ratio of the dual emission. Figure 2g shows the
average C-S-C angles in these conformations of the crystals.
We infer that solvent molecules with different sizes can facilitate
the deformation of the C-S bond to different degree. Once the
rigid crystals formed, the molecular conformation is fixed with
the removal of solvents (verified by the single-crystal analysis
without solvent molecules). The deformability of the C-S bond
induced the distinguishing intermolecular interactions among the
crystals (Figure 3a), resulting in different crystal confinement
environment.
For deeply understanding the photophysical mechanism, the
low-temperature (77 k) emission spectra of 1 was collected for
its altered states (Figure S13). For the monomeric state of 1 in
pure DMF, a smooth and broad phosphorescence band is
observed. In contrast, it is split in EA-ETH, TOU-BUT and ACN
crystals (Figure 2a, S14), reflecting the aggregated state only
contained one phosphorescent component that can be assigned
into vibrational structures rather than multiple species.[42]
Furthermore, the singlet-triplet energy gap (ΔEst) varies [24] little
among these crystals as described by the identical band
wavelength of both the fluorescence and phosphorescence in
Figure 2a. Another, the HOMO–LUMO orbital gap show little
separation as displayed by the typical conformations upon
computational simulation (Figure S15). Hence an effect of
twisted intra-molecular charge-transfer on the luminescence of
molecular crystals can be also excluded. [21] Therefore, it further
suggests that the photophysics of the crystals can be related to
the crystal restriction effect from the varied molecular
conformations which induced the different ISC effectiveness.
The conformational difference as well as the deformation of the
C-S bonds also resulted from the assistance of diverse non-
To better clarify such
a unique behaviour, we also
crystallized molecule 2 and selected two typical single-crystal
forms, namely an ACE–ETH crystal (from acetone and ethanol)
and an ACN crystal (from acetonitrile). Although both of the two
crystals exhibit a single symmetrical conformation, they still
show a polymorphism nature with the change of C-S-C bond
angles, similarly resulting in a tunable dual emission band as
well as an emission color difference (Figure 4). The symmetrical
conformation may be due to the strong O···H interaction (Figure
S21) originating from methoxy group between two adjacent
molecules. This interaction makes the system easy to form an
This article is protected by copyright. All rights reserved.

10.1002/anie.201900703
Angewandte Chemie International Edition
COMMUNICATION
edge-to-edge stacking, thus to avoid the close π–π stacking that
may cause the overcrowding of the molecules and the
unsymmetrical conformation like compound 1 (Figure S16-S20).
From the emission lifetime and spectra study (Figure S22 and
S23), we can also find it contains a triplet emission property.
Similarly to compound 1, the varied C-S-C angles imply a
different crystal enviroment and induced the fluorescence and
phosphorescence ratio tuning.
Figure 2. Single-crystal luminescence and conformational study of 1: (a) Emission spectra upon 365 nm excitation in DCM–IPR, EA–ETH, TOL–IPR, ACN, THF–
IPR and EA crystals. Inset shows the crystals photographs under a 365-nm UV lamp. (b) CIE 1931 chromaticity diagram signifying the luminescent color
coordinates for the corresponding crystals. PL lifetime in DCM–IPR crystal measured at (c) 420 nm, (d) 475 nm, 505 and 550 nm emission upon excitation at 365
nm. (e) Time-resolved emission spectra upon 365 nm excitation with delay of the DCM–IPR crystal. (f) Unit cell display of the symmetrical and the unsymmetrical
conformations of different crystals. The C-S-C bond angles are highlighted. (g) An average distribution of the C-S-C bond angles in the different conformations.
In addition to the ratio change between the fluorescence and
phosphorescence, an increase in luminescent quantum yield
(QY) was also observed among most of the crystals. [44] Namely,
a more rigid crystal environment can effectively enhance the ISC
process and reduce the non-radiative relaxation so as to
improve the emission efficiency, which can be explained by the
KISC (Table S1) and calculated SOC.[23] In addition, the P21 EA
crystal only exists in a stacking mode through a strong S–π
stacking instead of π–π stacking, as compared with the other P1
kind of crystals. This relatively deteriorated aggregation is
unfavorable for the emission efficiency. Table S2 shows the
average torsion (C-S-C dihedral angel) of the symmetrical and
unsymmetrical conformations in different crystals of 1.
Diminishing of the torsion reflects a strengthening of the
conformational coplanarity, which also facilitates molecular
rigidity for improving the QY.
With understanding the crystal nature, we turn to study the
related films for practical use. As a complete isolation all of the
conformations of compound
1 at film state by routine
approaches is not possible as compared with single crystals,
three typical solid films of compound 1 from ethanol (Eth film),
dichloromethane (DCM film) or ethyl acetate (EA film) were
straightforwardly obtained from the corresponding solution-
processing. Figure S24 shows a solid-state multi-band emission
of compound 1 in different films with proportional differences
among the crystalline forms. With a facile calculation through a
CIE Colorimetric diagram (Figure S25), a multi-color luminescent
property among these different solid-state materials can be
featured.
The dual-emission material here is highly sensitive to
mechanical stimuli.[45, 46] The dual-emission peaks of a typical EA
film of 1 greatly decreased during grinding (Figure 5a), with an
equilibrium state was reached after grinding for 30 s. The
This article is protected by copyright. All rights reserved.

10.1002/anie.201900703
Angewandte Chemie International Edition
COMMUNICATION
phosphorescent ratio here decreased more significantly than the
fluorescent one, because the grinding can weaken the crystal
rigidity (proved by the reduction of the XRD peaks, Figure 5c).
On the other hand, no emission blue-shift or red-shift was
observed in the ground film, suggesting that the excimer
formation in the grinding process can be excluded.
Figure 3. Crystal stacking modes with ISC regulation: Molecular packing display of (a) DCM–IPR, (b) TOU–BUT and (c) THF–IPR crystals. π–π, S–S,CH-π and
CH-F short-contacts were shown in these stacked molecular conformations. d) Spin-orbit matrix elements (cm-1) for the studied molecules calculated within
INSO/S approximation. The energy of S1 and T1 states (in eV) corresponds to the vertical excitations calculated by the (TD)DFT/B3LYP/6-31G(d).
Figure 4. Single-crystal luminescence and crystal conformational study of 2: (a) Emission spectra upon 365 nm excitation in ACE–ETH and ACN
crystals. The inset shows the crystal photographs under a 365-nm UV lamp. (b) Unit cell display of the conformations of different crystals. The C-S-C
bond angles are highlighted. (c) An average distribution of the C-S-C bond angles in the symmetrical conformations.
Such a mechanical response was also found to be reversible
and the initial emission signal could be restored when the film
was fumed with EA (see Figure 5a and 5b). Furthermore, the
crystalline peaks in the XRD spectra of the pristine film vanished
after grinding and could be restored by fuming (Figure 5c).
These results suggest that the molecular crystal form altered
along with luminescent color change during the mechanical
response process.
deformation of multiple C-S bond resulted in a varied
conformation that strongly connected to ISC to control the dual-
band ratio. Meanwhile, the molecular stacking mode in the
crystals plays a crucial role in regulating their emission efficiency.
Based on the multi-conformational control, in this way, a
manipulation
phosphorescence emission was accomplished making solid-
state multicolor emission adjustable and making
of
the
unimolecular
fluorescence
and
In conclusion, we have demonstrated a strategy for crystal
multi-conformational control of organic luminophore with a
regulation of their singlet and triplet emissive characteristics.
mechanoluminescence possible. We believe that this strategy
could be valuable for further exploitation of materials with
intrinsically tunable crystal-state emission with order and low
defect density.
Using
fluoro-substituted
tetrakis(arylthio)benzene-based
luminophores as a demonstration case, we found that the
This article is protected by copyright. All rights reserved.

10.1002/anie.201900703
Angewandte Chemie International Edition
COMMUNICATION
Figure 5. Reversible mechanoluminescence of 1: (a) Emission spectra of pristine, grinded and fumed EA film under 365 nm excitation. (b) The photographs of the
pristine and grinded EA film under daylight and 365-nm UV light. (c) PXRD traces of pristine, ground and fumed EA film.
[22] K. Upamali, L. A. Estrada, P. K. De, X. Cai, J. A. Krause, D. C. Neckers,
Langmuir, 2011, 27, 1573-1580.
[23] Y. Gong, G. Chen, Q. Peng, W. Yuan, Y. Xie, S. Li, Y. Zhang, B. Z. Tang,
Adv Mater, 2015, 27, 6195-6201.
[24] S. Hirata, Y. Sakai, K. Masui, H. Tanaka, S. Y. Lee, H. Nomura, N.
Acknowledgements
Nakamura, M. Yasumatsu, H. Nakanotani, Q. Zhang, K. Shizu, H.
Miyazaki, C. Adachi, Nat Mater, 2014, 14, 330-336.
[25] H. Qian, M. E. Cousins, E. H. Horak, A. Wakefield, M. D. Liptak, I.
This work was supported by 2017 Natural Science Foundation of
Shanghai (Grant No. 17ZR1402400), NSFC/China (21628401),
and the National Key Research and Development Program of
China (2017YFA0207700).
Aprahamian, Nat Chem, 2017, 9, 83-87.
[26] Y. Zhou, Y. Zhuang, X. Li, H. Ågren, L. Yu, J. Ding, L. Zhu, Chem Eur J,
2017, 23, 7642-7647.
[27] C. Tan, M. R. Pinto, M. E. Kose, I. Ghiviriga, K. S. Schanze, Adv Mater,
2004, 16, 1208-1212.
[28] a) L. Gu , H.g Shi , M. Gu , K. Ling, H. Ma, S. Cai, L. Song, C. Ma, H. Li,
G. Xing, X. Hang, J. Li, Y. Gao, W. Yao, Z. Shuai, Z. An, X. Liu, W.
Huang Angew. Chem. Int. Ed. 2018, 57, 8425-8431. b) c) W. Guan, S.
Wang, C. Lu, B. Z. Tang, Nat. Commun, 2016, 7, 11811.
[29] Z. Xie, C. Chen, S. Xu, J. Li, Y. S. Liu, J. Xu, Z. Chi, Angew Chem Int Ed,
2015, 54, 7181-7184.
Keywords: Crystal engineering • Noncovalent interactions •
Single-crystal conformation • Molecular Stacking •
Luminescence
[30] J. Yang, Z. Ren, Z. Xie, Y. Liu, C. Wang, Y. Xie, Q. Peng, B. Xu, W. Tian,
F. Zhang, Z. Chi, Q. Li, Z. Li, Angew Chem Int Ed, 2017, 56, 880-884.
[31] Z. F. An, C. Zheng, Y. Tao, R. F. Chen, H. F. Shi, T. Chen, Z. X. Wang,H.
H. Li, R. R. Deng, X. G. Liu, W. Huang, Nat Mater 2015, 14, 685-690.
[32] A. J. Tilley, R. D. Pensack, T. S. Lee, B. Djukic, G. D. Scholes, D. S.
Seferos. J Phys Chem C, 2014, 118, 9996-10004.
[33] Q. Zhang, J. Li, K. Shizu, S. Huang, S. Hirata, H. Miyazaki, C. Adachi, J
Am Chem Soc, 2012, 134, 14706-14709.
[34] L. Zhu, M. T. Trinh, L. Yin, Z. Zhang, Chem Sci, 2016, 7, 2058-2065.
[35] H. R. Tucker, M. Gingras, H. Brand, J. M. Lehn, J Chem Soc Perkin
Trans, 1997, 2, 1303-1307.
[36] a) H. Wu, Y. Zhou, L. Yin, C. Hang, X. Li, H. Ågren, T. Yi, Q. Zhang, L.
Zhu, J Am Chem Soc, 2017, 139, 785-791; b) M. Gingras, J. M.
Raimundo, Y. M. Chabre, Angew Chem Int Ed, 2006, 45, 1686-1712.
[37] A. Fermi, G. Bergamini, M. Roy, M. Gingras, P. Ceroni, J Am Chem Soc,
2014, 136, 6395-6400.
[38] G. Bergamini, A. Fermi, C. Botta, U. Giovanella, S. DiMotta, F. Negri, R.
Peresutti, M. Gingras, P. Ceroni, J Mater Chem C, 2013, 1, 2717-2724.
[39] R. Adams, A. Ferretti, J Am Chem Soc, 1959, 81, 4927-4931.
[40] H. Wu, C. Hang, X. Li, L. Yin, M. Zhu, J. Zhang, Y. Zhou, H. Ågren, Q.
Zhang, L. Zhu, Chem Commun, 2017, 53, 2661-2664.
[41] M. Sleiman, A. Varrot, J. M. Raimundo, M. Gingras, P. G. Goekjian,
Chem Commun, 2008, 48, 6507-6509.
[42] Z. He, W. Zhao, J. W. Lam, Q. Peng, H. Ma, G. Liang, Z. Shuai, B. Z.
Tang, Nature communications, 2017, 8, 416.
[1]
S. Tasch, O. Ekström, W. Graupner, G. Leising, P. Shlichting, U. Rohr,
Y. Geerts, U. Scherf, K. Müllen, Appl Phys Lett, 1997, 71, 2883-2885.
[2] B. W. D’Andrade, S. R Forrest, Adv Mater, 2004, 16, 1585-1595.
[3] CA. Zuniga, S. Barlow, S. R. Marder, Chem Mater, 2011 23, 658-681.
[4] C. W. Hsu, C. C. Lin, M. W. Chung, Y. Chi, G. H. Lee, P. T. Chou,; C.
Chang, P. Chen, J Am Chem Soc, 2011, 133, 12085-12099.
[5] H. A. Al-Attar, G. C. Griffiths, T. N. Moore, M. Tavasli, M. A. Fox, M. R.
Bryce, A. P. Monkman, Adv Funct Mater, 2011, 21, 2376-2382.
[6] Z. Jiang, Z. Zhong, S. Xue, Y. Zhou, Y. Meng, Z. Hu, N. Ai, J. Wang, J.
Peng, Y. Ma, J. Pei, J. Wang, Y. Cao, ACS Appl Mater Interfaces, 2014,
6, 8345-8352.
[7] E. Jang, S. Jun, H. Jang, J. Lim, B. Kim, Y. Kim. Adv Mater, 2010, 22,
3076-3080.
[8]
[9]
J. Bouffard,; Y. Kim, T. M Swager, R. Weissleder, S. A. Hilderbrand,
Org Lett, 2008, 10, 37-40.
L. Zhu, C. Y. Ang, X. Li, K. Nguyen, S. Y. Tan, H. Ågren, Y. Zhao, Adv
Mater, 2012, 24, 4020-4024.
[10] H. Shi, X. Ma, Q. Zhao, B. Liu, Q. Qu, Z. An, Y. Zhao, W. Huang, Adv
Funct Mater, 2014, 24, 4823-4830.
[11] Y. H. Kim, H. Cho, T. W. Lee, PNAS. 2016, 113, 11694-11702.
[12] Z. Zhang, B. Xu, J. Su, L. Shen, Y. Xie, H. Tian, Angew Chem Int Ed,
2011, 50, 11654-11657.
[13] S. Park, O. Kwon, S. Kim, S. Park, M. G. Choi, M. Cha, S. Y. Park, D.
J. Jang, J Am Chem Soc, 2005, 127, 10070-10074.
[14] W. Z. Yuan, X. Y. Shen, H. Zhao, L. Tang, P. Lu, C. Wang, Y. Liu, Z.
Wang, Q. Zheng, J. Z. Sun, Y. Ma, B. Z. Tang, J Phys Chem C, 2010,
114, 6090-6099.
[15] Y. Sagara, T. Kato, Angew Chem Int Ed, 2008, 47, 5175-5179.
[16] A. Sautter, C. Thalacker, F. Würthner, Angew Chem Int Ed, 2001, 40,
4425-4428.
[43] a) L. Bian, H. Shi, X. Wang, K. Ling, H. Ma, M. Li, Z. Cheng, C. Ma, S.
Cai, Q. Wu, N. Gan, X. Xu, Z. An, W. Huang. J. Am. Chem. Soc. 2018,
140, 10734-10739. b) G. V. Baryshnikov, R. R. Valiev, N. N. Karaush, V.
A. Minaeva, A. N. Sinelnikov, S. K. Pedersen, M. Pittelkow, B. F. Minaev,
H. Ågren, Phys. Chem. Chem. Phys., 2016, 18, 28040; c) G. V.
Baryshnikov, R. R. Valiev, B. F. Minaev, H. Ågren, New J. Chem., 2017,
41, 2717; d) G. V. Baryshnikov, R. R. Valiev, B. F. Minaev, H. Ågren,
New J. Chem., 2017, 41, 7621-7625. e) X. Li, L. Zhu, S. Duan, Y. Zhao,
H. Ågren, Phys Chem Chem Phys, 2014, 16, 23854-23860.
[17] A. Vieira, H. Gallardo, J. Barberá, P. Romero, J. L. Serrano, T. Sierra, J
Mater Chem, 2011, 21, 5916-5922.
[18] L. Zong, Y. Xie, C. Wang, J. R. Li, Q. Li, Z. Li, Chem Commun, 2016, 52,
11496-11499.
[19] H. Wu, P. Zhao, X. Li, W. Chen, H. Ågren, Q. Zhang, L. Zhu, ACS Appl
Mater Interfaces, 2017, 9, 3865-3872.
[20] Z. Q. Xie, B. Yang, F. Li, G. Cheng, L. L. Liu, G. D. Yang, H. Xu, L. Ye,
M. Hanif, S. Y. Liu, D. G. Ma, Y. G. Ma, J Am Chem Soc, 2005, 127,
14152-14153.
[44] J. Yang, X. Zhen, B. Wang, X. Gao, Z. Ren, J. Wang, Y. Xie, J. Li, K. Pu,
Z. Li, Nature communications, 2018, 9, 840.
[45] B. R. Crenshaw, M. Burnworth, D. Khariwala, A. Hiltner, P. T. Mather, R.
Simha, C. Weder, Macromolecules, 2007, 40, 2400-2408.
[46] T. Mutai, H. Satou, K. Araki, Nat Mater, 2005, 4, 685-687.
[21] A. Nagai, Y. Okabeb, Chem Commun, 2014, 50, 10052-10054.
This article is protected by copyright. All rights reserved.

10.1002/anie.201900703
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
The deformable carbon–sulfur (C–S)
bond with diverse non-covalent
interactions essentially drives the
crystal conformational distortion of
asterisk-shaped luminogen, the
fluorescence–phosphorescence of
which can be profoundly regulated by
such a crystal multi-conformational
control.
Hongwei Wu+,Weijie Chi+, Gleb
Baryshnikov, Bin Wu, Yifan Gong,
Dongxiao Zheng, Xin Li, Yanli Zhao,
Xiaogang Liu, Hans Ågren , and
Liangliang Zhu*
Page No. – Page No.
Crystal Multi-Conformational Control
Through Deformable Carbon–Sulfur
Bond for Singlet–Triplet Emissive
Tuning
This article is protected by copyright. All rights reserved.