Citation: Liu Xiaojing, Jia Yanrong, Jiang Hao, Gao Guanlei, Xia Min. Two Polymorphs of Triphenylamine-substituted Benzo[d]imidazole: Mechanoluminescence with Different Colors and Mechanofluorochromism with Emission Shifts in Opposite Direction[J]. Acta Chimica Sinica, ;2019, 77(11): 1194-1202. doi: 10.6023/A19080306 shu

Two Polymorphs of Triphenylamine-substituted Benzo[d]imidazole: Mechanoluminescence with Different Colors and Mechanofluorochromism with Emission Shifts in Opposite Direction

Engineering Research Center for Eco-dyeing and Finishing Technology of Textiles, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018

Corresponding author: Xia Min, xiamin@zstu.edu.cn
Received Date: 19 August 2019
Available Online: 21 November 2019

Figures(12)

Mechanofluorochromism (MFC) and mechanoluminescence (ML) are two types of significant solid-state optical phenomena which are closely dependent on conformations, packing modes and intermolecular interactions. Herein, through a three-step route involving aromatic nucleophilic substitution, reduction and oxidative cyclization in DMSO under air, a benzo[d]imidazole with triphenylamine and 4-cyanophenyl respectively located at C(2)- and N(1)-position is obtained in good yields. Two polymorphs TBIM_B and TBIM_G of 4-(2-(4-(diphenylamino)phenyl)-1H-benzo[d]imidazol-1-yl)benzonitrile (TBIM) corespondingly exhibit intense deep-blue (435 nm) and green fluorescence (505 nm). Under force stimuli, both polymorphs turn into amorphous phase with cyan fluorescence (457 nm). By fuming in solvent vapor or annealing treatment, only the ground TBIM_B sample can be completely restored into the original crystalline structure, the ground TBIM_G sample is just transformed into TBIM_Bcrystal. It is assumed that the enhanced energy barrier induced by the denser packing in TBIM_G crystal makes the conversion from in amorphous phase to crystalline one kinetically infeasible. The crystallography reveals that triphenylamine moiety in TBIM_G crystal is less restrained by intermolecular interactions than that in TBIM_B crystal, which results in the long-wavelength TICT emission in the former crystal and the short-wavelength LE emission in the latter one. In exposure to force stimuli, TBIM_B and TBIM_G crystals respectively give out the blue (432 nm) and green (500 nm) flash. It is revealed by crystallography that both polymorphs hold centrosymmetric space groups. DFT calculations based on the molecular couples with strong intermolecular interactions demonstrate that the close-to-zero net dipole moments occurs on these couples. Hence, neither piezoelectric effect nor excitation of molecules on cracked surfaces by discharges between molecular couples should account for the ML behaviors of these two polymorphs. Due to the readily force-induced cleavage of the two crystals by particular chain-shaped packing, the endogenous friction discharge caused by relative movements between cleavage planes would excite molecules on these planes, and this mechanism is assumed to be mainly responsible for the ML activity of the two crystals.
- mechanofluorochromism,
- mechanoluminescence,
- polymorphs,
- endogenous friction discharge,
- benzimidazole
1. [1]
  (a) Peng, B. Y.; Xu, S. D.; Chi, Z. G.; Zhang, X. Q.; Zhang, Y.; Xu, J. R. Prog. Chem. 2013, 25, 1805(in Chinese). (彭邦银, 许适当, 池振国, 张锡奇, 张艺, 许家瑞, 化学进展, 2013, 25, 1805.)(b) Di, B. H.; Chen, Y. L. Chin. Chem. Lett. 2018, 29, 245; (c) Yuan, Y.; Yuan, W.; Chen, Y. L. Sci. China Mater. 2016, 59, 507; (d) Yuan, W.; Yuan, Y.; Chen, Y. L. Acta Polym. Sinica 2016, 11, 1495(in Chinese). (袁伟, 袁媛, 陈于蓝, 高分子学报, 2016, 11, 1495.) (e) Yang, J.; Chi, Z.; Zhu, W.; Tang, B. Z.; Li, Z. Sci. China Chem. 2019, 62, 1090; (f) Li, Q.; Li, Z. Adv. Sci. 2017, 4, 1600484.
2. [2]
  (a) Dong, Y. Q.; Lam, J. W. Y.; Tan, B. Z. J. Phys. Chem. Lett. 2015, 6, 3429; (b) Chi, Z.; Zhang, X.; Xu, B.; Zhou, X.; Ma, C.; Zhang, Y.; Liu, S.; Xu, J. Chem. Soc. Rev. 2012, 41, 3878; (c) Wang, C.; Li, Z. Mater. Chem. Front. 2017, 1, 2174; (d) Yang, Z.; Chi, Z.; Mao, Zhang, Z. Y.; Liu, S.; Zhao, J. M.; Aldred, P.; Chi, Z. Mater. Chem. Front. 2018, 2, 861; (e) Varughese, S. J. Mater. Chem. C 2014, 2, 3499; (f) Sagara, Y.; Yamane, S.; Mitani, M.; Weder, C.; Kato, T. Adv. Mater. 2016, 28, 1073; (g) Bian, G. F.; Huang, H.; Zhan, L. L.; Lü, X. J.; Cao, F.; Zhang, C.; Zhang, Y. J. Acta Phys.-Chim. Sin. 2016, 32, 589(in Chinese). (边高峰, 黄华, 占玲玲, 吕晓静, 曹枫, 张诚, 张玉建, 物理化学学报, 2016, 32, 589.) (h) Sun, J. B.; Zhang, G. H.; Jia, X. Y.; Xue, P. C.; Jia, J. H.; Lu, R. Acta Chim. Sinica 2016, 74, 165(in Chinese). (孙静波, 张恭贺, 贾小宇, 薛鹏冲, 贾俊辉, 卢然, 化学学报, 2016, 74, 165); (i) Ouyang, M.; Yu, C. H.; Zhang, Y. J.; Hu, B.; Lü, X. J.; Sun, J. W.; Zhang, C. Acta Phys.-Chim. Sin. 2012, 28, 2944(in Chinese). (欧阳密, 俞春辉, 张玉建, 胡彬, 吕晓静, 孙璟玮, 张诚, 物理化学学报, 2012, 28, 2944.)
3. [3]
  (a) Seki, T.; Takamatsu, Y.; Ito, H. J. Am. Chem. Soc. 2016, 138, 6252; (b) Jin, M.; Seki, T.; Ito, H. J. Am. Chem. Soc. 2017, 139, 7452; (c) Yagai, S.; Okamura, S.; Nakano, Y.; Yamauchi, M.; Kishikawa, K.; Karatsu, T.; Kitamura, A.; Ueno, A.; Kuzuhara, D.; Yamada, H.; Seki, T.; Ito, H. Nat. Commun. 2014, 5, 4013.
4. [4]
  (a) Zheng, K.; Zheng, Y.; Peng, L.; Xiang, Y.; Tong, A. J. J. Phys. Chem. C 2017, 121, 21610; (b) Lü, Y.; Liu, Y.; Ye, X.; Liu, G. F.; Tao, X. T. CrystEngComm 2015, 17, 526; (c) Chung, K.; Kwon, M. S.; Leung, B. M.; Kim, J. S. ACS Cent. Sci. 2015, 1, 94.
5. [5]
  (a) Shi, P.; Duan, Y.; Wei, W.; Xu, Z.; Li, Z.; Han, T. J. Mater. Chem. C 2018, 6, 2476; (b) Feng, C.; Wang, K.; Xu, Y.; Liu, L.; Zou, B.; Lu, P. Chem. Commun. 2016, 52, 3836; (c) Wang, L.; Wang, K.; Zou, B.; Ye, K.; Zhang, H.; Wang, Y. Adv. Mater. 2015, 27, 2918; (d) Xie, W.-Z.; Zheng, H.-C.; Zheng, Y.-S. J. Mater. Chem. C 2017, 5, 10462.
6. [6]
  (a) Hirata, S.; Watanabe, T. Adv. Mater. 2006, 18, 2725; (b) Lim, S. J.; An, B. K.; Jung, S. D.; Chung, M. A.; Park, S. Y. Angew. Chem., Int. Ed. 2004, 43, 6346; (c) Olson, C. E.; Previte, M. J. R.; Fourkas, J. T. Nat. Mater. 2002, 1, 225; (d) Irie, M.; Fukaminato, T.; Sasaki, T.; Tamai, N.; Kawai, T. Nature 2002, 420, 759.
7. [7]
  (a) Kishimura, A.; Yamashita, T.; Yamaguchi, K.; Aida, T. Nat. Mater. 2005, 4, 546; (b) Zhu, X.; Liu, R.; Li, Y.; Huang, H.; Wang, Q.; Wang, D.; Zhu, X.; Liu, S.; Zhu, H. Chem. Commun. 2014, 50, 12951; (c) Qi, Q.; Liu, Y.; Fang, X.; Zhang, Y.; Chen, P.; Wang, Y.; Yang, B.; Xu, B.; Tian, W.; Zhang, S. X. RSC Adv. 2013, 3, 7996; (d) Kumar, P.; Dwivedi, J.; Gupta, B. K. J. Mater. Chem. C 2014, 2, 10468; (e) Lu, X.-L.; Xia, M. J. Mater. Chem. C 2016, 4, 9350.
8. [8]
  (a) Yuan, W. Z.; Tan, Y.; Gong, Y.; Lu, P.; Lam, J. W. Y.; Shen, X. Y.; Feng, C.; Sung, H. Y.; Lu, Y.; Williams, I. D.; Sun, J. Z.; Zhang, Y.; Tang, B. Z. Adv. Mater. 2013, 25, 2837; (b) Li, C.; Tang, X.; Zhang, L.; Li, C.; Liu, Z.; Bo, Z.; Dong, Y. Q.; Tian, Y.-H.; Dong, Y.; Tang, B. Z. Adv. Optical Mater. 2015, 3, 1184; (c) Naeem, K. C.; Subhakumari, A.; Varughese, S.; Nair, V. C. J. Mater. Chem. C 2015, 3, 10225; (d) Sun, J.; Han, J.; Liu, Y.; Duan, Y.; Han, T.; Yuan, J. J. Mater. Chem. C 2016, 4, 8276; (e) Xue, P.; Yang, Z.; Chen, P. J. Mater. Chem. C 2018, 6, 4994.
9. [9]
  (a) Sagara, Y.; Kato, T. Angew. Chem. Int. Ed. 2011, 50, 9128; (b) Yoon, S.-J.; Chung, J. W.; Gierschner, J.; Kim, K. S.; Choi, M.-G.; Kim, D.; Park, S. Y. J. Am. Chem. Soc. 2010, 132, 13675; (c) Sun, H.; Liu, S.; Lin, W.; Zhang, K. Y.; Lü, W.; Huang, W.; Huo, F.; Yang, H.; Jenkins, G.; Zhao, Q.; Huang, W. Nat. Commun. 2014, 5, 3601; (d) Zhang, K. Y.; Liu, S.; Zhao, Q.; Huang, W. Coord. Chem. Rev. 2016, 319, 180; (e) Chen, X.; Sun, G.; Zhang, T.; Liu, S.; Zhao, Q.; Huang, W. Adv. Mater. 2016, 28, 7137; (f) Zhao, Q.; Xu, W.; Sun, H.; Yang, J.; Zhang, K. Y.; Liu, S.; Ma, Y.; Huang, W. Adv. Opt. Mater. 2016, 4, 1167; (g) Lin, W.; Zhao, Q.; Sun, H.; Zhang, K. Y.; Yang, H.; Yu, Q.; Zhou, X.; Guo, S.; Liu, S.; Huang, W. Adv. Opt. Mater. 2015, 3, 368; (h) Han, J.; Sun, J.; Li, Y.; Duan, Y.; Han, T. J. Mater. Chem. C 2016, 4, 9287.
10. [10]
  (a) Xu, B.; Li, W.; He, J.; Wu, S.; Zhu, Q.; Yang, Z.; Wu, Y.-C.; Zhang, Y.; Jin, C.; Lu, P.-Y.; Chi, Z.; Liu, S.; Xu, J.; Bryce, M. R. Chem. Sci. 2016, 7, 5307; (b) Xu, S.; Liu, T.; Mu, Y.; Wang, Y.-F.; Chi, Z.; Lo, C.-C.; Liu, S.; Zhang, Y.; Lien, A.; Xu, J. Angew. Chem. 2015, 127, 888; (c) Yang, J.; Ren, Z.; Xie, Z.; Liu, Y.; Wang, C.; Xie, Y.; Peng, Q.; Xu, B.; Tian, W.; Zhang, F.; Chi, Z.; Li, Q.; Li, Z. Angew. Chem. Int. Ed. 2017, 56, 880; (d) Neen, K. K.; Sudhakar, P.; Dipak, K.; Thilagar, P. Chem. Commun. 2017, 53, 3641; (e) Xu, B.; He, J.; Mu, Y.; Zhu, Q.; Wu, S.; Wang, Y.; Zhang, Y.; Jin, C.; Lo, C.; Chi, Z.; Lien, A.; Liu, S.; Xu, J. Chem. Sci. 2015, 6, 3236; (f) Nakayama, H.; Nishida, J.; Takada, N.; Sato, H.; Yamashita, Y. Chem. Mater. 2012, 24, 671; (g) Nishida, J.; Ohura, H.; Kita, Y.; Hasegawa, H.; Kawase, T.; Takada, N.; Sato, H.; Sei, Y.; Yamashita, Y. J. Org. Chem. 2016, 81, 433; (h) Liu, M. L.; Wu, Q.; Shi, H. F.; An, Z. F.; Huang, W. Acta Chim. Sinica 2018, 76, 246(in Chinese). (刘明丽, 吴琪, 史慧芳, 安众福, 黄维, 化学学报, 2018, 76, 246.)
11. [11]
  (a) Wang, C.; Xu, B.; Li, M.; Chi, Z.; Xie, Y.; Li, Q.; Li, Z. Mater. Horiz. 2016, 3, 220; (b) Liu, F.; Tu, J.; Wang, X.; Wang, J.; Gong, Y.; Han, M.; Dang, X.; Liao, Q.; Peng, Q.; Li, Q.; Li, Z. Chem. Commun. 2018, 54, 5598.
12. [12]
  (a) Yang, J.; Ren, Z.; Chen, B.; Fang, M.; Zhao, Z.; Tang, B. Z.; Peng, Q.; Li, Z. J. Mater. Chem. C 2017, 5, 9242; (b) Yang, J.; Ren, Z.; Xie, Z.; Liu, Y.; Wang, C.; Xie, Y.; Peng, Q.; Xu, B.; Tian, W.; Zhang, F.; Chi, Z.; Li, Q.; Li, Z. Angew. Chem. Int. Ed. 2017, 56, 880.
13. [13]
  Xie, Z.; Yu, T.; Chen, J.; Ubba, E.; Wang, L.; Mao, Z.; Su, T.; Zhang, Y.; Aldred, M. P.; Chi, Z. Chem. Sci. 2018, 9, 5787. doi: 10.1039/C8SC01703D
14. [14]
  Hardy, G. E.; Baldwin, J. C.; Zink, J. I.; Kaska, W. C.; Liu, P.; Dubois, L. J. Am. Chem. Soc. 1977, 99, 3552. doi: 10.1021/ja00453a002
15. [15]
  Zink, J. I.; Chandra, B. P. J. Phys. Chem. 1982, 86, 5. doi: 10.1021/j100390a003
1. [1]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
2. [2]
  Zishuo Yi , Peng Liu , Yan Xu . Fluorescent “Chameleon”: A Popular Science Experiment Based on Dynamic Luminescence. University Chemistry, 2024, 39(9): 304-310. doi: 10.12461/PKU.DXHX202311079
3. [3]
  Cheng Zheng , Shiying Zheng , Yanping Zhang , Shoutian Zheng , Qiaohua Wei . Synthesis, Copper Content Analysis, and Luminescent Performance Study of Binuclear Copper (I) Complexes with Isomeric Luminescence Shift: A Comprehensive Chemical Experiment Recommendation. University Chemistry, 2024, 39(7): 322-329. doi: 10.3866/PKU.DXHX202310131
4. [4]
  Lin Song , Dourong Wang , Biao Zhang . Innovative Experimental Design and Research on Preparing Flexible Perovskite Fluorescent Gels Using 3D Printing. University Chemistry, 2024, 39(7): 337-344. doi: 10.3866/PKU.DXHX202310107
5. [5]
  Han ZHANG , Jianfeng SUN , Jinsheng LIANG . Hydrothermal synthesis and luminescent properties of broadband near-infrared Na₃CrF₆ phosphor. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 349-356. doi: 10.11862/CJIC.20240098
6. [6]
  Zijuan LI , Xuan LÜ , Jiaojiao CHEN , Haiyang ZHAO , Shuo SUN , Zhiwu ZHANG , Jianlong ZHANG , Yanling MA , Jie LI , Zixian FENG , Jiahui LIU . Synthesis of visual fluorescence emission CdSe nanocrystals based on ligand regulation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 308-320. doi: 10.11862/CJIC.20240138
7. [7]
  Xuewei BA , Cheng CHENG , Huaikang ZHANG , Deqing ZHANG , Shuhua LI . Preparation and luminescent performance of Sr_1-xZrSi₂O₇∶xDy³⁺ phosphor with high thermal stability. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 357-364. doi: 10.11862/CJIC.20240096
8. [8]
  Yan ZHAO , Jiaxu WANG , Zhonghu LI , Changli LIU , Xingsheng ZHAO , Hengwei ZHOU , Xiaokang JIANG . Gd³⁺-doped Sc₂W3O₁₂: Eu³⁺ red phosphor: Preparation and luminescence performance. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 461-468. doi: 10.11862/CJIC.20240316
9. [9]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
10. [10]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
11. [11]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
12. [12]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
13. [13]
  Wenjie SHI , Fan LU , Mengwei CHEN , Jin WANG , Yingfeng HAN . Synthesis and host-guest properties of imidazolium-functionalized zirconium metal-organic cage. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 105-113. doi: 10.11862/CJIC.20240360
14. [14]
  Minna Ma , Yujin Ouyang , Yuan Wu , Mingwei Yuan , Lijuan Yang . Green Synthesis of Medical Chemiluminescence Reagents by Photocatalytic Oxidation. University Chemistry, 2024, 39(5): 134-143. doi: 10.3866/PKU.DXHX202310093
15. [15]
  Qin Li , Kexin Yang , Qinglin Yang , Xiangjin Zhu , Xiaole Han , Tao Huang . Illuminating Chlorophyll: Innovative Chemistry Popularization Experiment. University Chemistry, 2024, 39(9): 359-368. doi: 10.3866/PKU.DXHX202309059
16. [16]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
17. [17]
  Yang YANG , Pengcheng LI , Zhan SHU , Nengrong TU , Zonghua WANG . Plasmon-enhanced upconversion luminescence and application of molecular detection. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 877-884. doi: 10.11862/CJIC.20230440
18. [18]
  Borong Yu , Huijiao Zhang , Xinyu Zhang , Xiaoying Li , Shuming Chen , Zhangang Han . The Blue Elf in the Dark: Gradient Science Popularization Experiments on Chemiluminescence. University Chemistry, 2024, 39(9): 295-303. doi: 10.12461/PKU.DXHX202403107
19. [19]
  Xiaxue Chen , Yuxuan Yang , Ruolin Yang , Yizhu Wang , Hongyun Liu . Adjustable Polychromatic Fluorescence: Investigating the Photoluminescent Properties of Copper Nanoclusters. University Chemistry, 2024, 39(9): 328-337. doi: 10.3866/PKU.DXHX202308019
20. [20]
  YanYuan Jia , Rong Rong , Jie Liu , Jing Guo , GuoYu Jiang , Shuo Guo . Unity is Strength, and Independence Shines: A Science Popularization Experiment on AIE and ACQ Effects. University Chemistry, 2024, 39(9): 349-358. doi: 10.12461/PKU.DXHX202402035

Get Citation

PDF

XML

Metrics

PDF Downloads(27)
Abstract views(1629)
HTML views(367)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142