N-type pyrazine and triazole-based luminogens with aggregation-enhanced emission characteristics

Article abstract of DOI:10.1039/c5cc03181h

N-type pyrazine-based 1,4- and 1,5-disubstituted 1,2,3-triazole derivatives, showing unique aggregation-enhanced emission characteristics, were facilely prepared via Cu- and Ru-catalysed azide-alkyne cycloadditions, respectively. Thanks to their electron-

Full text of DOI:10.1039/c5cc03181h

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N-type pyrazine and triazole-based luminogens with
aggregation-enhanced emission characteristics
Cite this: DOI: 10.1039/x0xx00000x
Ming Chen,a Lingzhi Li,a Han Nie,b Yang Shi,a Ju Mei,a Jian Wang,a Jin Zhi
Sun,a Anjun Qin*ab and Ben Zhong Tang*abc
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
deficient, but its electron property has not been revealed yet. Inspired
by this prospect, in this work, we expanded and systematically
investigated this pyrazine-based system in the hope to develop new
N-type AIEgens.
N-type pyrazine-based 1,4- and 1,5-disubstituted 1,2,3-
triazole derivatives, showing the unique aggregation-
enhanced emission characteristics, were facilely prepared by
the Cu- and Ru-catalysed azide-alkyne cycloadditions,
respectively. Thanks to their electron-deficient property,
they could readily form red-emissive charge transfer
complexes with electron-donating triphenylamine in the
aggregate and solid states.
Over the past decades, exploitation of new luminogens with
enhanced emission in the aggregate state has received considerable
interests for their potential applications in optoelectronic devices,
chemical sensors and biological probes.1 However, most of
conjugated organic molecules emit more efficiently in the solution
but the luminescence is weakened or quenched when aggregated,
that is, these molecules suffer from the notorious aggregation-caused
quenching (ACQ) effect.2
Chart 1. Chemical structures of representative P-type (red), neutral (black)
and N-type (blue) AIEgens.
Among the reported methods for tackling this difficulty, the
aggregation-induced emission (AIE), conceptually termed in 2001
by Tang et al. is promising because it can enable the naturally
occurred aggregation to play positive instead of negative roles in
enhancing the emission efficiency in the aggregate or solid states.3,4
The restriction intramolecular rotation (RIR) has been proved
experimentally and theoretically to its mechanism, which has been
widely adopted by researchers to explain their observed emission
behaviors of AIE-active luminogens (AIEgens).5
The AIE phenomenon has been attracting increasing interests
among the researchers worldwide. With their enthusiastic efforts
paid, hundreds of AIEgens with full color emission have been
developed and their potential high-tech applications in organic light-
emitting diodes, high sensitive and selective chemo- and bio-sensors,
etc. have been demonstrated.6,7
However, most of the developed AIEgens are electron-rich ones.
The electron-deficient (N-type) AIEgens are rare though they could
play indispensable roles in functions as electron transport and
electron acceptor materials (Chart 1).8 In 2009, we reported a new
type of pyrazine-based AIEgen, named 2,3-dicyano-5,6-
diphenylpyrazine (DCDPP), and unambiguously confirmed the RIR
mechanism of AIE by covalently “locking” its two phenyl rings.5c
Theoretically, the dicyanopyrazine moiety in DCDPP is electron-
During the course of chemical decoration of AIEgens, click
reaction was employed as it shares such fascinating merits as high
efficiency, regioselectivity and atom economy.9 For example,
tetraphenylethene (TPE)-cored AIEgens were readily and efficiently
prepared by us using Cu(I)-catalyzed azide-alkyne cycloaddition, a
typical click reaction. More importantly, thanks to the high polarity
and electron-withdrawing ability of formed 1,4-disubstituted 1,2,3-
triazole rings, the E/Z isomers were facilely isolated via column
chromatography for the first time. Using the pure isomers, the
plausible E/Z isomerization for the AIE mechanism was excluded.10
Moreover, 1,5-regioisomers could also be prepared by the azide-
alkyne click reaction in the presence of Cp*Ru(PPh3)2Cl.11 The
varying regioregularity of triazoles will endow them with distinctly
different property as demonstrated in our previous work.12
Nevertheless, few study has been carried out to investigate the effect
of regioregularity of triazole-based AIEgens on their properties. In
this work, we integrated pyrazine and triazole moieties together to
generate new N-type AIEgens and to investigate their interesting
properties.
The Cu(PPh3)3Br- and Cp*Ru(PPh3)2Cl-catalyzed click reactions
of 2,3-dicyano-5,6-bis(4-ethynylphenyl)pyrazine (1) and 1-(6-
azidohexyloxy)benzene (2) under mild reactions readily furnish 1,4-
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and 1,5-regioregular 3a and 3b in yields higher than 80%,
respectively [Scheme 1, see Electronic Supplementary Information,
(ESI)† for detailed synthetic procedures]. 3a and 3b are soluble in
commonly used organic solvents, such as THF, dichloromethane,
chloroform and insoluble in water. They are thermally stable. As can
be seen from Figure S1 (ESI†), the temperatures for 5% weight
losses are higher than 390 oC. However, they possess the glass
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DOI: 10.1039/C5CC03181H
o
transition temperatures of ca. 50 C probably due to the containing
alkyl chains.
Scheme 1. Synthetic routes to 1,4- and 1,5-regioregular triazole containing
pyrazine-based N-type AIEgens.
Their structures were fully characterized by spectroscopic
methods and satisfactory analysis data were obtained (Fig. S2-S8,
1
ESI†). We first measured their H NMR spectra in CDCl3 (Fig. S6,
ESI†), from which we found the resonance of ethynyl protons of 1 at
δ 3.27 was disappeared in 3a and 3b. However, the peaks severely
overlapped in the down-field, which makes the identification of
regioisomers difficult. Delightfully, in our previous work, we have
shown that the 1H NMR spectra of triazole-containing molecules and
polymers have better resolution in DMSO-d6 than that in CDCl3.12a
We thus re-measured the 1H NMR spectra of 3a and 3b in DMSO-d6
(Fig. S7, ESI†). From the spectra, we can find the protons of 1,4-
and 1,5-regioregular triazole resonated at
δ 8.68 and 7.96,
Figure 1. (A) PL spectra of 3a in THF/water mixtures with different water
fraction (fw); ex = 367 nm, [3a] = 10 M. (B) Changes in the fluorescence
quantum yield (F) of 3a and 3b in THF/water mixtures with fw. Inset:
photographs of 3a and 3b in THF/water mixtures with fw of 99%, which were
taken under a UV lamp.
respectively. Furthermore, no resonance proton signal of 1,5-
regioregular triazole was found in 3a (vice versa), indicating that
pure 1,4- and 1,5-regioisomers were obtained. 13
After confirming their structures, we studied their photo-physical
properties. The absorption spectra of 3a and 3b showed maximum
absorptions at 367 and 346 nm in THF, respectively (Table S1,
ESI†). Moreover, in solution, 3a emits at 474 nm, which has 16 nm
red-shift compared to 3b (Fig. 1A and Fig. S9, ESI†). The
theoretical calculation using DFT/B3LYP/6-31G(d,p) basis set also
showed that 1,4-isomer of 3a is structurally more planar than that of
1,5-isomer of 3b, and hence electronically more conjugated due to
the less steric effect between triazole rings and adjacent phenyl rings
(Table S2, ESI†).12a In addition, the emission of 3a and 3b red-
shifted compared to DCDPP (423 nm), manifesting that the triazole
rings have extended the conjugation of the resultant molecules.5c
DCDPP is AIE-active. Whether its derivatives of 3a and 3b behave
similarly? We measured their photoluminescence spectra and
quantum yield (F) in THF/water mixtures with different water
fractions (fw). Although the absorption of 3a and 3b changed little
with addition of water into their THF solutions (Fig. S10, ESI†), the
F nearly sustained to decrease until the fw reached to 60 and 70%,
accompanying with red-shifts of their emission peaks about 23 and
17 nm, respectively. This phenomenon could be reasonably
explained by a twisted intramolecular charge-transfer (TICT)
mechanism.14 Once the fw beyond these values, obvious enhanced F
values were observed, which became the largest at the fw of 95 and
99%, respectively (Fig. 1B), demonstrating an AIE activity. In this
stage, 3a and 3b begin to aggregate because the solvating power of
Figure 2. (A) Energy level diagram of 3a, 3b and TPA estimated by cyclic
voltammetry. (B) Photographs of 3a (a, e), 3b (b, f) and 3a/TPA (c, g) and
3b/TPA (d, h) in solid states taken under room lighting (a-d) and UV
illumination (e-h). All isomer/TPA mixtures are prepared with the molar ratio
of 1:1.
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thus leading to enhanced emissions. The 18 nm red-shift of emission
the aqueous mixture decrease, making the F enhanced due to the
RIR effect. Meanwhile, the TICT effect is efficiently weakened. This
mutual competition results in the enhancement of the emission and
F.
It is interesting to note that the F of 3a is much higher than that
of 3b both in the solution and aggregate states. The structure of 3b is
more congest than that of 3a, which offers it larger free volume for
the phenyl rings to rotate even in the aggregate state and hence
dissipate the energy of excited state non-radiatively.
of 3b/TPA in THF/water mixture is likely due to the lower LUMO
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energy level and more twisted structural conformation of 3b (Fig.
3B).15 Moreover, 3a/TPA and 3b/TPA (molDaOr Ir:a1t0io.10a3r9e/Cb5oCthC013:118)1iHn
the thin film states also emit in the red light region with peaks at ~
610 nm (Fig. S16, ESI†), indicating that charge-transfer process is a
universal phenomenon in the condensed phases.
In summary, N-type pyrazine-based 1,4- and 1,5-disubstituted
1,2,3-triazole derivatives of 3a and 3b were facilely synthesized by
Cu(PPh3)3Br- and Cp*Ru(PPh3)2Cl-catalyzed click reactions,
respectively. Both isomers possess higher F in aggregate states than
that in solution states, demonstrating an aggregation-enhanced
emission. The addition of water into their THF solutions showed
that the emission first decreased due to the TICT effect and then
increased because of the RIR process. Thanks to their strong
electron-withdrawing ability, their complexes with TPA readily red-
shifted their emission from 474 and 458 nm in solution to 617 and
633 nm in the aggregate states, respectively. This work not only
provides an efficient way to synthesize novel N-type AIEgens but
also demonstrates a new strategy to generate AIE systems with red
emission.
This work was partially supported by the key project of the
Ministry of Science and Technology of China (2013CB834702); the
National Science Foundation of China (21490571, 21222402 and
21174120); the Research Grants Council of Hong Kong (16301614,
N_HKUST604/14 and N_HKUST620/11). A.Q. and B.Z.T. thank
the support from Guangdong Innovative Research Team Program
(201101C0105067115).
As we discussed above, dicyanopyrazine and triazole moieties are
electron-withdrawing groups, which make 3a and 3b electron-
deficient, too.
To prove this interesting property, we first
characterized them using cyclic voltammetry (CV) technique. The
results (Fig. 2A and Fig. S11, ESI†) indicated that the LUMO
energy levels of 3a and 3b are deduced to be -3.28 and -3.39 eV,
respectively, which are much lower than that of conventional and
commercial electron transport materials, such as tri(8-
hydroxyquinoline) aluminum (Alq3, -3.0 eV) and 1,3,5-tris(N-
phenylbenzimidazole-2-yl)benzene (TPBi, -2.7 eV) (Table S1, ESI†),
demonstrating a typical N-type property. This trait endows AIEgens
containing such N-type structure with excellent electron transporting
property and also facilitates the electron injection from the LiF/Al
cathode if they are used to fabricate light-emitting diodes (OLEDs).
4
Water fraction
(vol %)
B
A
99
3
2
1
90
Notes and references
a
MOE Key Laboratory of Macromolecular Synthesis and
Functionalization, Department of Polymer Science and Engineering,
Zhejiang University, Hangzhou 310027, China. E-mail: qinaj@zju.edu.cn
(A.J.Q.).
3a/TPA
3b/TPA
b
Guangdong Innovative Research Team, State Key Laboratory of
540
585
630
Wavelength (nm)
675
720 90
92
94
96
98
100
Water fraction (vol%)
Luminescent Materials and Devices, South China University of
Technology, Guangzhou 510640, China.
Figure 3. (A) PL spectra of 3a/TPA in THF/water mixtures with fw from 90 to
99%. ex = 380 nm. (B) Changes of PL intensity (I/I0) of 3a/TPA and 3b/TPA
with fw. [3a] = [3b] = [TPA] = 10 M. Inset: photographs of 3a/TPA (left)
and 3b/TPA (right) in THF/water mixture with fw of 99%, which were taken
under a UV lamp.
c
Department of Chemistry, Institute for Advanced Study, Institute of
Molecular Functional Materials, and State Key Laboratory of Molecular
Neuroscience, The Hong Kong University of Science & Technology,
Clear Water Bay, Kowloon, Hong Kong China. E-mail: tangbenz@ust.hk
(B.Z.T.).
By taking advantage of their strong electron-withdrawing abilities,
we fabricated their complexes with strong electron-donating
molecule of triphenylamine (TPA). Mechanical trituration of 3a or
3b with TPA readily furnished homogeneous blends. Excitingly, the
†
Electronic Supplementary Information (ESI) available: Synthetic
details, 1H and 13C NMR spectra, absorption and photoluminescence
complexes gave conspicuous red fluorescence under the illumination spectra, and CV curves of 3a and 3b. See DOI: 10.1039/c000000x/
of a UV lamp (Fig. 2B). It is worth noting that new emission peaks
of 3a/TPA and 3b/TPA complexes were recorded at ~620 and 607
nm (Fig. S12 and S13, ESI†) in the solid states. Moreover, no
obvious variation of emission wavelength and intensity could be
observed through modest alerting of the mixed molar ratio of 3a or
3b with TPA.
To have a detailed understanding of this phenomenon, the photo-
physical property of the isomer/TPA complexes was investigated in
their aggregates. As depicted in Figure 3A and Figures S14 and S15
(ESI†), the absorption profiles of 3a/TPA and 3b/TPA remained
almost no changes in THF/water mixtures with fw of 90-99%. The
peaked emission intensities of 3a/TPA and 3b/TPA at ~617 and 633
nm in THF/water mixtures with fw of 90-99%, however, increase
linearly, respectively. With addition of water, the environment
surround the complexes become hydrophilic, which forces the
complexes to pack tightly and facilitates the charge-transfer and
restricts the intramolecular rotation of 3a and 3b at the same time,
1
(a) M. Shimizu and T. Hiyama, Chem. Asian J., 2010, 5, 1516; (b) C. W.
Tang and S. A. Vanslyke, Appl. Phys. Lett., 1987, 51, 913; (c)
Fluorescence Sensors and Biosensors, ed. R. B. Thompson, CRC, Boca
Raton, 2006.
2
3
J. B. Birks, Photophysics of Aromatic Molecules, Wiley, London, 1970.
J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, H. S. Kwok, X.
Zhan, Y. Liu, D. Zhu and B. Z. Tang, Chem. Commun., 2001, 1740.
For reviews, see: (a) R. R. Hu, N. L. Leung and B. Z. Tang, Chem. Soc.
Rev., 2014, 43, 4494; (b) J. J. Zhang, Q. Zou and H. Tian, Adv. Mater.,
2013, 25, 378; (c) Y. Z. Zhao, M. M. Cai, Y. Qian, L. H. Xie and W.
Huang, Prog. Chem., 2013, 25, 296; (d) D. Ding, K. Li, B. Liu and B. Z.
Tang, Acc. Chem. Res., 2013, 46, 2441; (e) Z. G. Chi, X. Q. Zhang, B. J.
Xu, X. Zhou, C. P. Ma, Y. Zhang, S. W. Liu and J. R. Xu, Chem. Soc.
Rev., 2012, 41, 3878; (f) A. J. Qin, J. W. Y. Lam and B. Z. Tang, Prog.
Polym. Sci., 2012, 37, 182; (g) M. Wang, G. Zhang, D. Zhang, D. Zhu
and B. Z. Tang, J. Mater. Chem., 2010, 20, 1858; (h) Y. Hong, J. W. Y.
Lam and B. Z. Tang, Chem. Commun., 2009, 4332; (i) Y. Hong, J. W.
4
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Page 4 of 5
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Y. Lam and B. Z. Tang, Chem. Soc. Rev., 2011, 40, 5361; (j) J. Mei, Y.
Chem. Rev., 2009, 109, 5620.
N. Hong, J. W. Y. Lam, A. J. Qin, Y. H. Tang and B. Z. Tang, Adv. 10 J. Wang, J. Mei, R. Hu, J. Z. Sun, A. Qin and B. Z. Tang, J. Am. Chem.
Mater., 2014, 26, 5429; (k) H. Wang, E. Zhao, J. W. Y. Lam and B. Z.
Tang, Mater. Today, 2015, DOI: 10.1016/j. mattod.2015.03.004.
Soc., 2012, 134, 9956.
11 A. Qin, J. W. Y. Lam and B. Z. Tang, Chem. SDoOc.I:R1e0v.1.,023091/C0,53C9C,023512821H
View Article Online
5
(a) S. L. Deng, T. L. Chen, W. L. Chien and J. L. Hong, J. Mater. Chem. 12 (a) A. Qin, J. W. Y. Lam, C. K. W. Jim, L. Zhang, J. Yan, M. Häussler, J.
C, 2014, 2, 651; (b) Y. Liu, Y. Tang, N. N. Barashkov, I. S. Irgibaeva, J.
W. Y. Lam, R. Hu, D. Birimzhanova, Y. Yu and B. Z. Tang, J. Am.
Chem. Soc., 2010, 132, 13951; (c) A. Qin, J. W. Y. Lam, M. Faisal, C.
K. W. Jim, L. Tang, J. Sun, H. H. Y. Sung, I. D. Williams and B. Z.
Liu, Y. Dong, D. Liang, E. Chen, G. Jia and B. Z. Tang,
Macromolecules, 2008, 41, 3808; (b) Q. Wang, M. Chen, B. Yao, J.
Wang, J. Mei, J. Z. Sun, A. Qin and B. Z. Tang, Macromol. Rapid
Commun., 2013, 34, 796.
Tang, Appl. Phys. Lett., 2009, 94, 253308; (d) Z. Li, Y. Q. Dong, J. W. 13 (a) Q. Wang, H. Li, Q. Wei, J. Z. Sun, J. Wang, X. A. Zhang, A. Qin and
Y. Lam, J. Sun, A. Qin, M. Häuβler, Y. P. Dong, H. H. Y. Sung, I. D.
Williams, H. S. Kwok and B. Z. Tang, Adv. Funct. Mater., 2009, 19,
905; (e) G. Yu, S. Yin, Y. Liu, J. Chen, X. Xu, X. Sun, D. Ma, X. Zhan,
B. Z. Tang, Polym. Chem., 2013, 4, 1396; (b) Y. Liu, J. Wang, D.
Huang, J. Zhang, S. Guo, R. Hu, Z. Zhao, A. Qin and B. Z. Tang,
Polym. Chem., 2015, DOI: 10.1039/c5py00186b.
Q. Peng, Z. Shuai, B. Z. Tang, D. Zhu, W. Fang and Y. Luo, J. Am. 14 R. Hu, E. Lager, A. Aguilar-Aguilar. J. Liu, J. W. Y. Lam, H. H. Y.
Chem. Soc., 2005, 127, 6335; (f) J. Chen, C. W. Law, J. W. Y. Lam, Y.
Dong, S. Lo, I. D. Williams, D. Zhu and B. Z. Tang, Chem. Mater.,
2003, 15, 1535.
Sung, I. D. Williams, Y. Zhong, K. S. Wong, E. Peña-Cabrera and B.
Z. Tang, J. Phys. Chem. C, 2009, 113, 15845.
15 J. H. Kim, B.-K. An, S.-J. Yoon, S. K. Park, J. E. Kwon, C.-K. Lim,
and S. Y. Park, Adv. Funct. Mater., 2014, 24, 2746.
6
(a) C. T. Lai and J. L. Hong, J. Phys. Chem. B, 2010, 114, 10302; (b) X.
Xue, Y. Zhao, L. Dai, X. Zhang, X. Hao, C. Zhang, S. Huo, J. Liu, C.
Liu, A. Kumar, W. Chen, G. Zou and X. Liang, Adv. Mater., 2014, 26,
712; (c) C. J. Bhongale, C. W. Chang, C. S. Lee, E. W. G. Diau and C.
S. Hsu, J. Phys. Chem. B, 2005, 109, 13472; (d) Z. Xie, B. Yang, W.
Xie, L. Liu, F. Shen, H. Wang, X. Yang, Z. Wang, Y. Li, M. Hanif, G.
Yang, L. Ye and Y. Ma, J. Phys. Chem. B, 2006, 110, 20993; (e) X.
Zhang, X. Zhang, L. Tao, Z. Chi, J. Xu and Y. Wei, J. Mater. Chem. B.,
2014, 2, 4398; (f) J. Huang, N. Sun, Y. Dong, R. Tang, P. Lu, P. Cai, Q.
Li, D. Ma, J. Qin and Z. Li, Adv. Funct. Mater., 2013, 23, 2329; (g) M.
Shimizu, K. Mochida and T. Hiyama, Angew. Chem. Int. Ed., 2008, 47,
9760; (h) X. Hou, Y. Wu, H. Cao, H. Sun, H. Li, G. Shan and Z. Su,
Chem. Commun., 2014, 50, 6031; (i) A. Shao, Z. Guo, S. Zhu, S. Zhu, P.
Shi, H. Tian and W. Zhu, Chem. Sci., 2014, 5, 1383; (j) Z. T. Wang, Y.
Fang, J. Z. Sun, A. Qin and B. Z. Tang, Sci. China Chem., 2013, 56,
1187; (k) X. Shen, G. Huang, K. Li, G. Zhang and D. Q. Zhang, Sci.
China Chem., 2013, 56, 1197; (l) M. Chen, L. Li, H. Nie, J. Tong, L.
Yan, B. Xu, J. Z. Sun, W. Tian, Z. Zhao, A. Qin and B. Z. Tang, Chem.
Sci., 2015, 6, 1932.
7
(a) L. Chen, Y. B. Jiang, H. Nie, P. Lu, H. H. Y. Sung, I. D. Williams, H.
S. Kwok, F. Huang, A. J. Qin, Z. J. Zhao and B. Z. Tang, Adv. Funct.
Mater., 2014, 24, 3621; (b) J. Liu, J. W. Y. Lam and B. Z. Tang, J.
Inorg. Organomet. Polym. Mater., 2009, 19, 249; (c) Z. Zhao, J. W. Y.
Lam and B. Z. Tang, J. Mater. Chem., 2012, 22, 23726; (d) W. Dong, T.
Fei, A. Palma-Cando and U. Scherf, Polym. Chem., 2014, 5, 4048; (e)
K. R. Ghosh, S. K. Saha and Z. Y. Wang, Polym. Chem., 2014, 5, 5638;
(f) Z. Wang, K. Ma, B. Xu, X. Li and W. Tian, Sci. China Chem., 2013,
56, 1234; (g) J. T. He, B. Xu, F. P. Chen, H. J. Xia, K. P. Li, L. Ye and
W. J. Tian, J. Phys. Chem. C, 2009, 113, 9892; (h) H. Li, Z. Chi, X.
Zhang, B. Xu, S. Liu, Y. Zhang and J. Xu, Chem. Commun., 2011, 47,
11273; (i) J. W. Chen, B. Xu, X. Y. Ouyang, B. Z. Tang and Y. Cao, J.
Phys. Chem. A., 2004, 108, 7522; (j) T. Han, Y. J. Zhang, X. Feng, Z. G.
Lin, B. Tong, J. B. Shi, J. G. Zhi and Y. P. Dong, Chem. Commun.,
2013, 49, 7049; (k) Y. X. Guo, X. Feng, T. Y. Han, S. Wang, Z. G. Lin,
Y. P. Dong and B. Wang, J. Am. Chem. Soc., 2014, 136, 15485.
(a) Y. Liu, X. Ye, G. Liu, Y. Lv, X. Zhang, S. Chen, J. W. Y. Lam, H. S.
Kwok, X. Tao and B. Z. Tang, J. Mater. Chem. C, 2014, 2, 1004; (b) Z.
Zhao, P. Lu, J. W. Y. Lam, Z. Wang, C. Y. K. Chan, H. H. Y. Sung, I.
D. Williams, Y. Ma and B. Z. Tang, Chem. Sci., 2011, 2, 672; (c) Z.
Yang, Z. Chi, T. Yu, X. Zhang, M. Chen, B. Xu, S. Liu, Y. Zhang and J.
Xu, J. Mater. Chem., 2009, 19, 5541; (d) J. Mei, J. Wang, J. Z. Sun, H.
Zhao, W. Yuan, C. Deng, S. Chen, H. H. Y. Sung, P. Lu, A. Qin, H. S.
Kwok, Y. Ma, I. D. Williams and B. Z. Tang, Chem. Sci., 2012, 3, 549;
(e) Q. Zhao, S. Zhang, Y. Liu, J. Mei, S. Chen, P. Lu, A. Qin, Y. Ma, J.
Z. Sun and B. Z. Tang, J. Mater. Chem., 2012, 22, 7387; (f) L. Zöphel,
V. Enkelmann and K. Müllen, Org. Lett. 2013, 15, 804; (g) Y. Xu, B.
Li, W. Li, J. Zhao, S. Sun and Y. Pang, Chem. Commun., 2013, 49,
4764.
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(a) H. C. Kolb, M. G. Finn and K. B. Sharpless, Angew. Chem., Int. Ed.,
2001, 40, 2004; (b) W. Xi, T. F. Scott, C. J. Kloxin and C. N. Bowman,
Adv. Funct. Mater., 2014, 24, 2572; (c) P. Thirumurugan, D. Matosiuk
and K. Jozwiak, Chem. Rev., 2013, 113, 4905; (d) R. K. Iha, K. L.
Wooley, A. M. Nyström, D. J. Burke, M. J. Kade and C. J. Hawker,
4 | J. Name., 2012, 00, 1‐3
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N-type pyrazine-based 1,4- and 1,5-disubstituted 1,2,3-triazole
derivatives, showing the unique aggregation-enhanced emission
characteristics, were facilely prepared by the Cu- and Ru-catalysed click
reactions. The resultant AIEgens could readily form red-emissive
complexes with triphenylamine in the aggregate and solid states.
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