4,4'-二甲氧基三苯胺取代偶氮苯开关分子的设计合成、电化学及光化学性质研究

doi:10.6023/cjoc201902015

有机化学 ›› 2019, Vol. 39 ›› Issue (7): 2009-2017.DOI: 10.6023/cjoc201902015 上一篇下一篇

所属专题：有机超分子化学合辑

研究论文

4,4'-二甲氧基三苯胺取代偶氮苯开关分子的设计合成、电化学及光化学性质研究

鄢剑锋^a, 张睿祺^a, 原野^a, 袁耀锋^a,b

a 福州大学化学学院福州 350116;
b 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002

收稿日期:2019-02-18 修回日期:2019-03-10 发布日期:2019-03-21
通讯作者: 袁耀锋 E-mail:yaofeng_yuan@fzu.edu.cn
基金资助:
国家自然科学基金（No.21772023）、中国科学院福建物质结构研究所结构化学国家重点实验室基金（No.20180020）和福州大学贵重仪器设备开放测试基金（No.2018T006）资助项目.

4,4'-Dimethoxy-triphenylamine Conjugated Azobenzene Photochromic Switches:Synthesis, Electrochemical and Photoisomerization Studies

Yan Jianfeng^a, Zhang Ruiqi^a, Yuan Ye^a, Yuan Yaofeng^a,b

a College of Chemistry, Fuzhou University, Fuzhou 350116)(b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002

Received:2019-02-18 Revised:2019-03-10 Published:2019-03-21
Contact: 10.6023/cjoc201902015 E-mail:yaofeng_yuan@fzu.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21772023), the Research Fund for the State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (No. 20180020) and the Valuable Instrument and Equipment Open Test Fund of Fuzhou University (No. 2018T006).

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摘要/Abstract

通过Pd催化的Sonogashira偶联合成了三个以4，4'-二甲氧基三苯胺基团为氧化还原中心的偶氮苯化合物4～6，电化学和光谱电化学的研究表明，该类化合物具有优秀的氧化还原可逆性.光致异构的实验表明，三苯胺基团在偶氮苯上的取代位置对该类化合物的光化学性质有显著的影响.化合物4不仅可以通过光照实现顺式到反式的异构化，也可仅通过改变三苯胺基团的价态高效地实现.

关键词: 三苯胺, 偶氮苯, 光致异构, 氧化还原

Three azobenzenes 4~6 conjugated with 4,4'-dimethoxy-triphenylamine redox center have been synthesized by palladium-catalyzed Sonogashira coupling reactions in moderate yield after column chromatographic purification. They are all stable when exposed in air and moisture in both the solid and solution state. The ¹H NMR spectra of 4~6 showned that the azobenzene groups are in the trans configuration. The UV/Vis spectra of the target molecule were studied. The UV/Vis absorption bands of 4~6 are less clearly separated, which is similar to those for aminoazobenzen or pseudostilbene. The absorption bands at the π→π^* band of 4 and 6 are redshifted, due to the strong electronic interaction between the azobenzene unit and the para-triphenylamine unit, which results in the formation of a longer conjugation system than the corresponding meta isomers. Electrochemical and spectroelectrochemical studies indicate excellent redox reversibility of these compounds. Significant spectra change upon the process of redox makes these compounds have potential applications of electrochemical switching. Among the derivatives, compound 4 exhibits the highest cis form (45%) in the photostationary state (PSS) upon light irradiation at 435 nm. The photoisomerization studies indicate that the photochemistry properties is strongly influenced by the substituted position of the triphenylamine moiety. Photoisomerization studies showed that these compounds have fast photoisomerization rate due to the higher photoisomerization quantum yield, which is an order of magnitude larger than that of ferrocenyl (ethynyl) azobenzenes. Both compounds 4 and 6 exhibit excellent fatigue resistance and reversibility under several repeated reversible isomerization cycles. The cis-to-trans photoisomerization of 4 can be not only achieved by irradiation at UV lignt, but also realized by a more efficient way of change the state of redox center. Our study will provide a good basis for research in design new type of multiple-response molecular switches.

Key words: triphenylamine, azobenzene, photoisomerization, redox

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鄢剑锋, 张睿祺, 原野, 袁耀锋. 4,4'-二甲氧基三苯胺取代偶氮苯开关分子的设计合成、电化学及光化学性质研究[J]. 有机化学, 2019, 39(7): 2009-2017.

Yan Jianfeng, Zhang Ruiqi, Yuan Ye, Yuan Yaofeng. 4,4'-Dimethoxy-triphenylamine Conjugated Azobenzene Photochromic Switches:Synthesis, Electrochemical and Photoisomerization Studies[J]. Chin. J. Org. Chem., 2019, 39(7): 2009-2017.

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[1] (a) Klajn, R.; Stoddart, J. F.; Grzybowski, B. A. Chem. Soc. Rev. 2010, 39(6), 2203.
(b) Natali, M.; Giordani, S. Chem. Soc. Rev. 2012, 41(10), 4010.
(c) Bleger, D.; Hecht, S., Angew. Chem., Int. Ed. 2015, 54(39), 11338.
[2] (a) Beharry, A. A.; Woolley, G. A. Chem. Soc. Rev. 2011, 40(8), 4422.
(b) Bandara, H. M. D.; Burdette, S. C. Chem. Soc. Rev. 2012, 41, 1809.
(c) Yan, J.-F. Ph.D. Dissertation, Fuzhou University, Fuzhou, 2015(in Chinese). (鄢剑锋, 博士论文, 福州大学, 福州, 2015.)
[3] (a) Sakamoto, A.; Hirooka, A.; Namiki, K.; Kurihara, M.; Murata, M.; Sugimoto, M.; Nishihara, H. Inorg. Chem. 2005, 44, 7547.
(b) Kume, S.; Nishihara, H. Metal-based Photoswitches Derived from Photoisomerization Photofunctional Transition Metal Complexes, Ed.:Yam, V., Springer Berlin/Heidelberg, 2007, Vol. 123, p. 79.
(c) Bianchi, A.; Delgado-Pinar, E.; García-España, E.; Giorgi, C.; Pina, F. Coord. Chem. Rev. 2013, 260, 156.
(d) Moustafa, M. E.; McCready, M. S.; Puddephatt, R. J. Organometallics 2013, 32, 2552.
(e) Samanta, A.; Ravoo, B. J. Chem. Eur. J. 2014, 20, 4966.
[4] (a) Maciejewski, A.; Jaworska-Augustyniak, A.; Szeluga, Z.; Wojtczak, J.; Karolczak, J. Chem. Phys. Lett. 1988, 153, 227.
(b) Kikuchi, M.; Kikuchi, K.; Kokubun, H. Bull. Chem. Soc. Jpn. 1974, 47, 1331.
(c) Farmilo, A.; Wilkinson, F. Chem. Phys. Lett. 1975, 34, 575.
(d) Lee, E. J.; Wrighton, M. S. J. Am. Chem. Soc. 1991, 113, 8562.
(e) Fery-Forgues, S.; Delavaux-Nicot, B. J. Photochem. Photobiol., A 2000, 132, 137.
[5] Sakamoto, R.; Kume, S.; Nishihara, H. Chem. Eur. J. 2008, 14(23), 6978.
[6] (a) Seo, E. T.; Nelson, R. F.; Fritsch, J. M.; Marcoux, L. S.; Leedy, D. W.; Adams, R. N. J. Am. Chem. Soc. 1966, 88, 3498.
(b) Reynolds, R.; Line, L. L.; Nelson, R. F. J. Am. Chem. Soc. 1974, 96(4), 1087.
[7] Gritzner, G.; Kuta, J. Pure Appl. Chem. 1984, 56(4), 461.
[8] Dei, D. K.; Lund, B. R.; Wu, J.; Simon, D.; Ware, T.; Voit, W. E.; MacFarlane, D.; Liff, S. M.; Smith, D. W. ACS Macro Lett. 2012, 2, 35.
[9] Tanino, T.; Yoshikawa, S.; Ujike, T.; Nagahama, D.; Moriwaki, K.; Takahashi, T.; Kotani, Y.; Nakano, H.; Shirota, Y. J. Mater. Chem. 2007, 17, 4953.
[10] (a) Blevins, A. A.; Blanchard, G. J. J. Phys. Chem. B 2004, 108, 4962.
(b) Rau, H. In Photochromism, Ed.:Dürr, H.; Bouas-Laurent, H., Elsevier Science, Amsterdam, 2003, p. 165.
[11] (a) Lambert, C.; Noll, G.; Schelter, J. Nat. Mater. 2002, 1(1), 69.
(b) Sreenath, K.; Suneesh, C. V.; Gopidas, K. R.; Flowers, R. A. J. Phys. Chem. A 2009, 113, 6477.
(c) Lambert, C.; Nöll, G. J. Am. Chem. Soc. 1999, 121, 8434.
(d) Chen, M.; Yang, S.; Zheng, J.; Xu, C. Acta Chim. Sinica 2013, 71, 713(in Chinese). (陈梅, 杨树威, 郑建明, 徐春叶, 化学学报, 2013, 71, 713.)
(e) Feng, J.; Shao, J.; Gong, Z.; Zhong, Y. Chin. J. Org. Chem. 2016, 36, 2407(in Chinese). (冯骏, 邵将洋, 龚忠亮, 钟羽武, 有机化学, 2016, 36, 2407.)
[12] (a) Moustafa, M. E.; McCready, M. S.; Puddephatt, R. J. Organometallics 2012, 31, 6262.
(b) Wazzan, N. A.; Richardson, P. R.; Jones, A. C. Photochem. Photobiol. Sci. 2010, 9, 968.
[13] Yan, J.-F.; Lin, D.-Q.; Wang, X.-G.; Wu, K.-Q.; Xie, L.-L.; Yuan, Y.-F., Chem. Asian J. 2015, 10, 614.
[14] Horie, M.; Sakano, T.; Osakada, K.; Nakao, H. Organometallics 2004, 23, 18.
[15] Asano, T.; Okada, T.; Shinkai, S.; Shigematsu, K.; Kusano, Y.; Manabe, O. J. Am. Chem. Soc. 1981, 103, 5161.
[16] (a) Helmut, K. In CRC Handbook of Organic Photochemistry and Photobiology, Vols. 1& 2, CRC Press, Boca Raton, 2003.
(b) Yager, K. G.; Barrett, C. J. In Intelligent Materials, Chapter 17, The Royal Society of Chemistry, Cambridge, 2008, p. 424.
(c) García-Amorós, J.; Velasco, D. Beilstein J. Org. Chem. 2012, 8, 1003.

4,4'-二甲氧基三苯胺取代偶氮苯开关分子的设计合成、电化学及光化学性质研究

4,4'-Dimethoxy-triphenylamine Conjugated Azobenzene Photochromic Switches:Synthesis, Electrochemical and Photoisomerization Studies

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