具有聚集诱导发光效应及高对比度可逆力致变色三芳基丙烯腈化合物的设计、合成及性能

doi:10.6023/cjoc201306017

有机化学 ›› 2014, Vol. 34 ›› Issue (1): 161-169.DOI: 10.6023/cjoc201306017 上一篇下一篇

研究论文

具有聚集诱导发光效应及高对比度可逆力致变色三芳基丙烯腈化合物的设计、合成及性能

毛文纲, 陈康, 欧阳密, 孙璟玮, 周永兵, 王永胜, 宋庆宝, 张诚

浙江工业大学化学工程与材料学院绿色化学合成技术国家重点实验室培育基地杭州 310014

收稿日期:2013-06-09 修回日期:2013-08-20 发布日期:2013-09-06
通讯作者: 宋庆宝,张诚 E-mail:qbsong@zjut.edu.cn; czhang@zjut.edu.cn
基金资助:
国家重点基础研究发展计划（973计划，Nos. 2010CB635108，2011CBA00700）；国际科技合作重点项目计划（No. 2012DFA51210）和中国国家自然科学基金（Nos. 51203138，51273179）资助项目.

Design, Synthesis and Characterization of Triarylacrylonitrile Compounds Exhibiting Aggregation-Induced Emission and High Contrast Reversible Mechanochromism

Mao Wengang, Chen Kang, Ouyang Mi, Sun Jingwei, Zhou Yongbing, Wang Yongsheng, Song Qingbao, Zhang Cheng

a State Key Laboratory Breeding Base for Green Chemistry Synthesis Technology, College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310014

Received:2013-06-09 Revised:2013-08-20 Published:2013-09-06
Supported by:
Project supported by the National Key Basic Research Program of China (973 Program, Nos. 2010CB635108, 2011CBA00700), the International Sci & Tech Cooperation Program (No. 2012DFA51210) and the National Natural Science Foundation of China (Nos. 51203138, 51273179).

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摘要/Abstract

设计、合成了两个三芳基丙烯腈化合物（Z）-2，3-二-[4，4'-（二苯胺）苯基]-3-苯基丙烯腈（2DPA-TPCN）和（Z）-2，3-二-[4，4'-（二苯胺）联苯基]-3-苯基丙烯腈（2TPA-TPCN），利用核磁共振（NMR）、质谱（EI-MS）等对它们进行了结构表征. 通过混合溶剂四氢呋喃（THF）/水析出实验显示，化合物2DPA-TPCN和2TPA-TPCN在纯THF溶剂中几乎无荧光，而在THF/水混合溶剂中，当水体积分数增加（f_w>60%）时呈现聚集荧光增强现象. 对2DPA-TPCN和2TPA-TPCN粉末进行研磨后，发现它们的发光颜色分别从橙黄色（Φ_F=12.0%）变成橘红色（Φ_F=2.0%）和从翠绿色（Φ_F=44.6%）变成橘黄色（Φ_F=16.8%），且2TPA-TPCN的颜色变化在自然光下肉眼清晰可辨；研磨后的样品暴露在溶剂蒸气中或100 ℃放置2 min均能恢复到初始颜色. 以上现象表明2DPA-TPCN和2TPA-TPCN具有高对比度的可逆力致变色性质. SEM，XRD，DSC，荧光量子效率等测试结果表明其光学性质（荧光光谱、荧光寿命和量子效率等）发生变化是由分子聚集态的堆积模式的改变导致的，而研磨后的样品具有可逆性色变的根本原因可能是其存在热力学亚稳态. 热重分析表明化合物有很好的热稳定性（2TPA-TPCN，T_d=436.4 ℃；2DPA-TPCN，T_d=387.6 ℃）.

关键词: 力致变色, 可逆, 荧光材料, 分子堆积, 三芳基丙烯腈

Two triarylacrylonitrile compounds, (Z)-2,3-bis(4-(diphenylamino)phenyl)-3-phenyl acrylonitrile (2DPA-TPCN) and (Z)-2,3-bis(4'-(diphenylamino)biphenyl-4-yl)-3-phenyl acrylonitrile (2TPA-TPCN) have been designed and synthesized. Characterizations were performed via nuclear magnetic resonance (NMR) and electron ionization-mass spectrometry (EI-MS). Exhibiting aggregation-induced emission (AIE) activity, the obtained 2DPA-TPCN and 2TPA-TPCN hardly have any luminescence in pure THF solution. However, strong luminescences were observed after adding water to the THF solutions (f_w>60%). When 2DPA-TPCN and 2TPA-TPCN were ground, their colors and intensity turned weakly from saffron [fluorescence quantum efficiency (Φ_F)=2.0%] to orange (Φ_F=12.0%) and from jade green (Φ_F=44.6%) to croci (Φ_F=16.8%), respectively. And the change of the color of 2TPA-TPCN could be discriminated at natural light. Moreover, the ground powder returns to original colour by being exposed to solvent vapor or being heated at about 100 ℃ for 2 min. Photoluminescence (PL) spectra of the samples, which were obtained under different conditions (ungrind and grind), showed that the maximum emission wavelength (λ_em) had a significant red-shift as high as 8 and 39 nm after being ground, respectively. The morphological structures of 2DPA-TPCN and 2TPA-TPCN under different aggregative state were observed by scanning electron microscopy (SEM). The results indicate that the damage on the surface morphology, which was caused by external stimuli, could be restored by being exposed to ethanol vapor or heated. The X-ray diffractometry (XRD) measurements show that the dye that was not ground displays indicative of well-defined microcrystalline-like structures and the grinding dye shows amorphous features in this state. These observations further indicate that the optical properties (PL spectra, Φ_F, fluorescence lifetime) of changes originate from the altering molecular packing mode from the high-order to disorder by being ground. The differential scanning calorimetry (DSC) measurements indicate that the grinding samples which have cold crystal peaks are thermodynamical metastable, while the other states are thermodynamical stable. These results further demonstrate that the primary cause of the reversibility of the grind sample might be the thermodynamical metastable. Furthermore, the thermal decomposition temperatures of 2DPA-TPCN and 2TPA-TPCN is 387.6 and 436.4 ℃ by thermogravimetry (TG) measurement, respectively, which indicates that the compounds have very good thermal stability.

Key words: mechanochromism, reversible, fluorescent material, molecular packing, triarylacrylonitrile

引用此文

毛文纲, 陈康, 欧阳密, 孙璟玮, 周永兵, 王永胜, 宋庆宝, 张诚. 具有聚集诱导发光效应及高对比度可逆力致变色三芳基丙烯腈化合物的设计、合成及性能[J]. 有机化学, 2014, 34(1): 161-169.

Mao Wengang, Chen Kang, Ouyang Mi, Sun Jingwei, Zhou Yongbing, Wang Yongsheng, Song Qingbao, Zhang Cheng. Design, Synthesis and Characterization of Triarylacrylonitrile Compounds Exhibiting Aggregation-Induced Emission and High Contrast Reversible Mechanochromism[J]. Chin. J. Org. Chem., 2014, 34(1): 161-169.

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[1] Mutai, T.; Satou, H.; Araki, K. Nat. Mater. 2005, 4, 685.

[2] Park, S. J.; Kuang, S. G.; Fryd, M.; Saven, J. G.; Park, S. J. J. Am. Chem. Soc. 2010, 132, 9931.

[3] Dong, Y. Q.; Lam, J. W. Y.; Qin, A. J.; Liu, J. Z.; Li, Z.; Tang, B. Z. Appl. Phys. Lett. 2007, 91, 011111.

[4] Ning, Z.; Chen, Z.; Zhang, Q.; Yan, Y.; Qian, S.; Cao, Y.; Tian, H. Adv. Funct. Mater. 2007, 17, 3799.

[5] Löwe, C.; Weder, C. Adv. Mater. 2002, 14, 1625.

[6] Srinivasan, S.; Babu, P. A.; Mahesh, S.; Jayaghosh, A. A. J. Am. Chem. Soc. 2009, 131, 15122.

[7] Sagara, Y.; Kato, T. Nat. Chem. 2009, 1, 605.

[8] Chi, Z. G.; Zhang, X. Q.; Xu, B. J.; Zhou, X.; Ma, C. P.; Zhang, Y.; Liu, S. W.; Xu, J. R. Chem. Soc. Rev. 2012, 41, 3878.

[9] Song, K.; Kuzmany, H.; Wallraff, G. M.; Miller, R. D.; Rabolt, J. F. Macromolecules 1990, 23, 3870.

[10] Song, K.; Miller, R. D.; Wallraff, G. M.; Rabolt, J. F. Macromolecules 1991, 24, 4084.

[11] Song, K.; Miller, R. D.; Wallraff, G. M.; Rabolt, J. F. Macromolecules 1992, 25, 3629.

[12] Chan, H. S. O.; Ng, S. C. Prog. Polym. Sci. 1998, 23, 1167.

[13] Yamamoto, T.; Sato, T.; Iijima, T.; Abe, M.; Fukumoto, H.; Koizumi, T. A.; Usui.; M.; Nakamura, Y.; Yagi, T.; Tajima, H..; Okada, T.; Sasaki, S.; Kishida, H.; Nakamura, A.; Fukuda, T.; Emoto, A.; Ushijima, H.; Kurosaki, C.; Hirota, H. Bull. Chem. Soc. Jpn. 2009, 82, 896.

[14] Zhang, X. Q.; Chi, Z. G.; Zhang, Y.; Liu, S. W.; Xu, J. R. J. Mater. Chem. C 2013, 1, 3376.

[15] Fridman, N.; Speiser, S.; Kaftory, M. Cryst. Growth Des. 2006, 6, 1653.

[16] Gawinecki, R.; Viscardi, G.; Barni, E.; Hanna, M. A. Dyes Pigm. 1993, 23, 73.

[17] Weder, C. Nature 2009, 459, 45.

[18] Xu, B. J.; Xie, M. Y.; He, J. J.; Xu, B.; Chi, Z. G.; Tian, W. J.; Jiang, L.; Zhao, F.; Zhang, Y.; Xu, Z. Z.; Xu, J. R. Chem. Commun. 2013, 49, 273.

[19] Zhang, Z. L.; Yao, D. D.; Zhou, T. L.; Zhang, H. Y.; Wang, Y. Chem. Commun. 2011, 47, 7782.

[20] Teng, M. J.; Jia, X. R.; Yang, S.; Chen, X. F.; Wei, Y. Adv. Mater. 2012, 24, 1255.

[21] Jakubiak, R.; Collison, C. J.; Wan, W.; Rothberg, L. J.; Hsieh, B. R. J. Phys. Chem. A 1999, 103, 2394.

[22] Luo, J. D.; Xie, Z. L.; Lam, J. Y.; Cheng, L.; Chen, H. Y.; Qiu, C. F.; Kwok, H. S.; Zhan, X. W.; Liu, Y. Q.; Zhu, D. B.; Tang, B. Z. Chem. Commun. 2001, 1740.

[23] An, B. K.; Kwon, S. K.; Jung, S. D.; Park, S. Y. J. Am. Chem. Soc. 2002, 124, 14410.

[24] Luo, J. F.; Wang, X. H.; Wang, X. M.; Su, W. M. Chin. J. Chem. 2012, 30, 2488 (in Chinese).

[25] Mi, B. X.; Dong, Y. Q.; Li, Z.; Lam, J. W. Y.; Häußler, M.; Sung, H. H. Y.; Kwok, H. S.; Dong, Y. P.; Williams, I. D.; Liu, Y. Q.; Luo, Y.; Shuai, Z. G.; Zhu, D. B.; Tang, B. Z. Chem. Commun. 2005, 3583.

[26] Ning, Z.; Chen, Z.; Zhang, Q.; Yan, Y.; Qian, S.; Cao, Y.; Tian, H. Adv. Funct. Mater. 2007, 17, 3799.

[27] Li, Z.; Dong, Y. Q.; Lam, J. W. Y.; Sun, J.; Qin, A.; Häußler, M.; Dong, Y. P.; Sung, H. H. Y.; Williams, I. D.; Kwok, H. S.; Tang, B. Z. Adv. Funct. Mater. 2009, 19, 905.

[28] Toal, S. J.; Jones, K. A.; Magde, D.; Trogler, W. C. J. Am. Chem. Soc. 2005, 127, 11661.

[29] Liu, Y.; Tang, Y. H.; Barashkov, N. N.; Irgibaeva, I. S.; Lam, J. W. Y.; Hu, R. R.; Birimzhanova, D.; Yu, Y.; Tang, B. Z. J. Am. Chem. Soc. 2010, 132, 13951.

[30] Wang, M.; Zhang, G. X.; Zhang, D. Q.; Zhu, D. B.; Tang, B. Z. J. Mater. Chem. 2010, 20, 1858.

[31] Liu, Y.; Deng, C. M.; Tang, L.; Qin, A. J.; Hu, R. R.; Sun, J. Z.; Tang, B. Z. J. Am. Chem. Soc. 2011, 133, 660.

[32] Zhao, G. S.; Shi, C. X.; Guo, Z. Q.; Zhu, W. H.; Zhu, S. Q. Chin. J. Org. Chem. 2012, 32, 1620 (in Chinses).

(赵国生, 史川兴, 郭志前, 朱为宏, 朱世琴, 中国化学, 2012, 32, 1620.)

[33] 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.

[34] Gu, X. G.; Yao, J. J.; Zhang, G. X.; Yan, Y. L.; Zhang, C.; Peng, Q.; Liao, Q.; Wu, Y. S.; Xu, Z. Z.; Zhao, Y. S.; Fu, H. B.; Zhang, D. Q. Adv. Funct. Mater. 2012, 22, 4862.

[35] Luo, X. L.; Li, J. N.; Li, C. H.; Heng, L. P.; Dong, Y. Q.; Liu, Z. P.; Zhi, S. B.; Tang, B. Z. Adv Mater. 2011, 23, 3261.

[36] Zhou, X.; Li, H. Y.; Chi, Z. G.; Zhang, X. Q.; Zhang, Y.; Liu, S. W.; Jia, X. R. J. Fluoresc. 2012, 22, 565.

[37] Zhou, X.; Li, H. P.; Chi, Z. G.; Zhang, X. Q.; Zhang, J. Y.; Xu, B. J.; Zhang, Y.; Liu, S. W.; Jia, X. R. New J. Chem. 2012, 36, 685.

[38] Luo, X. L.; Zhao, W. J.; Shi, J. P.; Li, C. H.; Liu, Z. P.; Zhi, S. B.; Dong, Y. Q.; Tang, B. Z. J. Phys. Chem. C 2012, 116, 21967.

[39] Yoon, S. J.; Park, S. Y. J. Mater. Chem. 2011, 21, 8338.

[40] Dou, C. D.; Han, L.; Zhao, S. S.; Zhang, H. Y.; Wang, Y. J. Phys. Chem. Lett. 2011, 2, 666.

[41] Li, H.; Chi, Z. G.; Xu, B.; Zhang, X.; Li, X.; Liu, S.; Zhang, Y.; Xu, J. J. Mater. Chem. 2011, 21, 3760.

[42] Xu, B. J.; Chi, Z. G.; Zhang, X. Q.; Li, H. Y.; Chen, C. J.; Liu, S. W.; Zhang, Y.; Xu, J. R. Chem. Commun. 2011, 47, 11080.

[43] Wang, Y. L.; Wei, L.; Bu, L. Y.; Li, L. F.; Zheng, M.; Zhang, D. T.; Sun, M. X.; Tao, Y.; Xue, S. F.; Yang, W. J. J. Mater. Chem. C 2013, 1, 856.

[44] Yuan, W. Z.; Gong, Y. Y.; Chen, S. M.; Chen, X. Y.; Lam, J. W. Y.; Lu, P.; Lu, Y. W.; Wang, Z. M.; Hu, R. R.; Xie, N.; Kwok, H. S.; Zhang, Y. M.; Jing, Z. S.; Tang, B. Z. Chem. Mater. 2012, 24, 1518.

[45] Zhang, Y. J.; Sun, J. W.; Bian, G. F.; Chen, Y. Y.; Ouyang, M.; Hu, B.; Zhang, C. Photochem. Photobiol. Sci. 2012, 11, 1414.

[46] Zhang, Y. J.; Zhang, G. L.; Ouyang, M.; Hu, B.; Song, Q. B.; Sun, J. W.; Zhang, C.; Gu, C.; Xu, Y. X.; Ma, Y. G. Dyes Pigm. 2013, 98, 486.

[47] Mao, W. G.; Chen, K.; Ouyang, M.; Sun, J. W.; Zhou, Y. B.; Song, Q. B.; Zhang, C. Acta Chim. Sinica 2013, 71, 613 (in Chinese).

(毛文纲, 陈康, 欧阳密, 孙璟玮, 周永兵, 宋庆宝, 张诚, 化学学报, 2013, 71, 613.)

[48] Auweter, H.; Haberkorn, H.; Heckmann, W.; Horn, D.; Lüddecke, E.; Rieger, J.; Weiss, H. Angew. Chem., Int. Ed. 1999, 38, 2188.

[49] Jenekhe, S. A.; Osaheni, J. A. Science 1994, 265, 765.

[50] Zhang, X. Q.; Chi, Z. G.; Li, H. Y.; Xu, B. J.; Li, X. F.; Zhou, W.; Liu, S. W.; Zhang, Y.; Xu, J. R. Chem. Asian J. 2011, 6, 808.

[51] Crosby, G. A.; Demas, J. N. J. Phys. Chem. 1971, 75, 991.

具有聚集诱导发光效应及高对比度可逆力致变色三芳基丙烯腈化合物的设计、合成及性能

Design, Synthesis and Characterization of Triarylacrylonitrile Compounds Exhibiting Aggregation-Induced Emission and High Contrast Reversible Mechanochromism

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