蒽桥联的胺-胺电子耦合研究
收稿日期: 2016-06-13
修回日期: 2016-07-17
网络出版日期: 2016-08-10
基金资助
国家自然科学基金（Nos.21271176，21472196，21521062，21501183）和中国科学院战略性先导科技专项（No.XDB12010400）资助项目
Amine-Amine Electronic Coupling through an Anthracene Bridge
Received date: 2016-06-13
Revised date: 2016-07-17
Online published: 2016-08-10
Supported by
Project supported by the National Natural Science Foundation of China (Nos.21271176, 21472196, 21521062, 21501183), and the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB12010400).
合成了1，5-二（对甲氧基二苯胺）蒽（1）、2，6-二（对甲氧基二苯胺）蒽（2）和9，10-二（对甲氧基二苯胺）蒽（3）三种化合物，对它们的电化学、吸收和发射光谱、光谱电化学以及胺-胺电子耦合开展研究.三种化合物在+0.6~+1.0 V vs Ag/AgCl区域存在两步可逆氧化还原过程，两个氧化还原过程电位差△E在100 mV左右.单电子氧化产物1·+在近红外区域观测到弱价间电荷转移吸收（IVCT），电子耦合常数Vab估算为600 cm-1.化合物3·+观测到强IVCT吸收，其Vab估算为1440 cm-1.单电子氧化产物2·+则没有观测到明显IVCT吸收，表明有机胺在蒽桥基上的取代位置对胺-胺电子耦合程度有重要的影响.
冯骏 , 邵将洋 , 龚忠亮 , 钟羽武 . 蒽桥联的胺-胺电子耦合研究[J]. 有机化学, 2016 , 36(10) : 2407 -2412 . DOI: 10.6023/cjoc201606020
Three diamine compounds with an anthracene bridge were synthesized and characterized, including 1,5-bis(di-p-anisylamine)anthracene (1), 2,6-bis(di-p-anisylamine)anthracene (2) and 9,10-bis(di-p-anisylamine)anthracene (3). The elec-trochemistry, absorption and emission spectra, spectroelectrochemistry, and amine-amine electronic coupling of these compounds were examined. All compounds display two consecutive redox couples in the potential region between +0.6 and +1.0 V vs Ag/AgCl, with a potential splitting △E of around 100 mV. In the one-electron-oxidized state, weak intervalence charge transfer (IVCT) transitions were observed for 1·+ in the near-infrared (NIR) region and the electronic coupling parameter Vab was calculated to be 600 cm-1. In contrast, compound 3·+ displays an intense IVCT band in the NIR region with a Vab value of 1440 cm-1. However, no distinct IVCT band was discernable for 2·+, indicative of an eligible electronic coupling. This work demonstrates that the positions of the amine substituents on the anthracene bridge play a critical role in determining the degree of amine-amine electronic coupling.
Key words： amines; charge transfer; electrochemistry; photochemistry
[1] Creutz, C.; Taube, H. J. Am. Chem. Soc. 1969, 91, 3988.
[2] (a) Kong, D.-D.; Xue, L.-S.; Jang, R.; Liu, B.; Meng, X.-G.; Jin, S.; Ou, Y.-P.; Hao, X.; Liu, S.-H. Chem. Eur. J. 2015, 21, 9895. (b) Zhang, J.; Sun, C.-F.; Zhang, M.-X.; Hartl, F.; Yin, J.; Yu, G.-A.; Rao, L.; Liu, S. H. Dalton Trans. 2016, 45, 768.
[3] Zhang, D.-B.; Wang, J.-Y.; Wen, H.-M.; Chen, Z.-N. Organometallics 2014, 33, 4738.
[4] Tang, J.-H.; Shao, J.-Y.; He, Y.-Q.; Wu, S.-H.; Yao, J.; Zhong, Y.-W. Chem. Eur. J. 2016, 22, 10341.
[5] Zhong, Y.-W.; Gong, Z.-L.; Shao, J.-Y.; Yao, J. Coord. Chem. Rev. 2016, 312, 22.
[6] Hildebrandt, A.; Lang, H. Organometallics 2013, 32, 5640.
[7] Gong, Z.-L.; Zhong, Y.-W. Sci. China Chem. 2015, 58, 1444.
[8] Chen, T.; Tan, Y. N.; Zhang, Y.; Zhang, Y. Y.; Meng, M.; Lei, H.; Chen, L.; Liu, C. Y. Chem. Eur. J. 2015, 21, 2353.
[9] (a) Tang, J.-H.; Yao, C.-J.; Cui, B.-B.; Zhong, Y.-W. Chem. Rec. 2016, 16, 754. (b) Shao, J.-Y.; Yao, C.-J.; Cui, B.-B.; Gong, Z.-L.; Zhong, Y.-W. Chin. Chem. Lett. 2016, 27, 1105.
[10] (a) Wu, X.; Wu, Y.; Zhang, C.; Nie, H.; Lei, L.; Qin, C.; Wang, C.; Bai, X.; Wang, W. RSC Adv. 2015, 5, 58843. (b) Ma, X.; Wu, Y.; Wen, H.; Niu, H.; Wang, C.; Qin, C.; Bai, X.; Lei, L.; Wang, W. RSC Adv. 2016, 6, 4564.
[11] Fan, H.; Zhu, X. Sci. China Chem. 2015, 58, 922.
[12] Xiao, J.; Shi, J.; Li, D.; Meng, Q. Sci. China Chem. 2015, 58, 221.
[13] Tao, Y.; Yang, C.; Qin, J. Chem. Soc. Rev. 2011, 40, 2943.
[14] Yao, L.; Yang, B.; Ma, Y.-G. Sci. China Chem. 2014, 57, 335.
[15] (a) Hankache, J.; Wenger, O. S. Chem. Rev. 2011, 111, 5138. (b) Heckmann, S.; Lambert, C. Angew. Chem., Int. Ed. 2012, 51, 326.
[16] Shen, J.-J.; Shao, J.-Y.; Zhu, X.; Zhong, Y.-W. Org. Lett. 2016, 18, 256.
[17] Yoshizawa, M.; Klosterman, J. K. Chem. Soc. Rev. 2014, 43, 1885.
[18] Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Chem. Rev. 2012, 112, 2208.
[19] Guan, C.; Qian, Y. Chin. J. Org. Chem. 2014, 34, 537(in Chinese). (管成飞, 钱鹰, 有机化学, 2014, 34, 537.)
[20] Wang, B.; Qian, Y. Chin. J. Org. Chem. 2014, 34, 210(in Chinese). (王彬彬, 钱鹰, 有机化学, 2014, 34, 210.)
[21] Lambert, C.; Risko, C.; Coropceanu, V.; Schelter, J.; Amthor, S.; Gruhn, N. E.; Durivage, J. C.; Bredas, J.-L. J. Am. Chem. Soc. 2005, 127, 8508.
[22] (a) Su, Y.; Wang, X.; Li, Y.; Song, Y.; Sui, Y.; Wang, X. Angew. Chem., Int. Ed. 2015, 54, 1634. (b) Wang, X.; Zhang, Z.; Song, Y.; Su, Y.; Wang, X. Chem. Commun. 2015, 51, 11822.
[23] Vila, N.; Zhong, Y.-W.; Henderson, J. C.; Abruna, H. D. Inorg. Chem. 2010, 49, 796.
/
| 〈 |
|
〉 |
