具有大的双光子吸收截面的A-A-A型双苯乙烯基苯类化合物

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (11): 2222.

具有大的双光子吸收截面的A-A-A型双苯乙烯基苯类化合物

黄池宝1,2, 任安祥2, 李海渤2, 阳年发1

1. 湘潭大学化学学院, 环境友好化学与应用教育部重点实验室, 湘潭 411105;
2. 韶关大学英东生物工程学院农业工程系, 韶关 512005

收稿日期:2010-01-18 出版日期:2010-11-10 发布日期:2010-11-10
通讯作者: 阳年发, 男, 博士, 教授, 博士生导师, 主要从事有机合成研究. E-mail: nfyang@stu.edu.cn
基金资助:
国家自然科学基金(批准号: 20772102)和中国博士后科学基金(批准号: 20100471224)资助.

Synthesis of Bis(styryl)benzene Derivatives of Typical A-A-A Conjugation Structure with Large Two-photon Absorption Cross Sections

HUANG Chi-Bao1,2, REN An-Xiang2, LI Hai-Bo2, YANG Nian-Fa1*

1. Key Laboratory of Environmentally Friendly Chemistry and Applications, Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China;
2. Department of Agricultural Engineering, Yingdong Bioengineering College, Shaoguan University, Shaoguan 512005, China

Received:2010-01-18 Online:2010-11-10 Published:2010-11-10
Contact: YANG Nian-Fa. E-mail: nfyang@stu.edu.cn
Supported by:
国家自然科学基金(批准号: 20772102)和中国博士后科学基金(批准号: 20100471224)资助.

摘要/Abstract

摘要： 合成了A-A-A型双苯乙烯基苯类化合物FR[2,5-二氰基-1,4-二(4′-氟苯乙烯基)苯], 并采用核磁共振、红外光谱和元素分析等手段对其进行了表征. 用飞秒脉冲诱导荧光光谱法分别研究了两个A-A-A型双苯乙烯基苯类化合物FR与CY[2,5-二氰基-1,4-二(4′-氰基苯乙烯基)苯]以及两个D-A-D型双苯乙烯基苯类化合物MO[2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯]和MA[2,5-二氰基-1,4-二(4′-二甲胺基苯乙烯基)苯]的单、双光子吸收与发射特性. 实验结果表明, 最大单光子吸收与发射波长随末端取代基供电子能力的增强而增大, 末端强吸电子基化合物FR和CY具有相当高的荧光量子产率(分别为0.92与0.89)、较长的荧光寿命(分别为5.8与6.1 ns)及较大的双光子吸收系数(分别为19.1与20.5). 末端带强吸电子基的化合物FR与CY的双光子吸收截面(δ, 分别为6350 GM和6870 GM)较末端带供电子基的化合物MO和MA的δ(分别为270 GM与1790 GM)要大得多, 表明A-A-A型双苯乙烯基苯类化合物具有异常大的δ.

关键词: 双光子吸收, 双苯乙烯基苯衍生物, A-A-A型共轭结构, 双光子吸收截面

Abstract: The synthesis of FR[2,5-dicyano-1,4-bis-(4′-fluorostyryl)benzene] with typical A-A-A conjugation structure was reported, and its structure was characterized by 1H NMR, IR and elemental analysis. One- and two-photon absorption and emission properties of bis(styryl)benzene derivatives including FR and CY[2,5-dicyano-1,4-bis-(4′-cyanostyryl)benzene] with A-A-A conjugation structure, and MO[2,5-dicyano-1,4-bis-(4′-methoxystyryl)benzene] and MA[2,5-dicyano-1,4-bis-(4′-dimethylaminostyryl)benzene] with D-A-D conjugation structure were studied by the one- and two-photon-induced fluorescence emission in femtosecond pulses, respectively. The maximum wavelengths of the one-photonabsorption and emission increased with increasing electron-donating capacity of terminal substituent groups, and compounds FR and CY of electron-accepting terminal groups displayed very high fluorescence quantum yields(0.92 and 0.89, respectively), long fluorescence lifetime(5.8 and 6.1 ns, respectively) and large two-photon absorption coefficient(19.1 and 20.5, respectively). The two-photon absorption cross sections(δ) of FR and CY(6350 GM and 6870 GM, respectively) with strongly electron-accepting terminal groups were much larger than those of MO and MA(270 GM and 1790 GM, respectively) with electron-donating terminal groups. The result indicates that bis(styryl)benzene derivatives with A-A-A conjugation structure exhibit a considerably large δ.

Key words: Two-photon absorption, Bis(styryl)benzene derivative, A-A-A conjugation structure, Two-photon absorption cross section

TrendMD:

黄池宝, 任安祥, 李海渤, 阳年发. 具有大的双光子吸收截面的A-A-A型双苯乙烯基苯类化合物. 高等学校化学学报, 2010, 31(11): 2222.

HUANG Chi-Bao, REN An-Xiang, LI Hai-Bo, YANG Nian-Fa* . Synthesis of Bis(styryl)benzene Derivatives of Typical A-A-A Conjugation Structure with Large Two-photon Absorption Cross Sections. Chem. J. Chinese Universities, 2010, 31(11): 2222.

参考文献

[1]He G. S., Bhawalkar J. D., Zhao C. F., Prasad P. N.. Appl. Phys. Lett.[J], 1995, 67: 2433—2435 [2]He G. S., Yuan L., Cheng N., Bhawalkar J. D., Prasad P. N., Brott L. L., Clarson S. J., Reinhardt B. A.. J. Opt. Soc. Am. B[J], 1997, 14: 1079—1087 [3]Reinhardt B. A., Brott L. L., Clarson S. J., Dillard A. G., Bhatt J. C., Kannan R., Yuan L., He G. S., Prasad P. N.. Chem. Mater.[J], 1998, 10: 1863—1874 [4]Ehrlich J. B., Wu X. L., Lee I. Y. S., Hu Z. Y., Rckel H., Marder S. R., Perry J. W.. Opt. Lett.[J], 1997, 22: 1843—1845 [5]Albota M., Beljonne D., Bredas J. L., Ehrlich J. E., Fu J. Y., Heikal A. A., Hess S. E., Kogej T., Levin M. D., Marder S. R., McCord-Maughon D., Perry J. W., Rockel H., Rumi M., Subramaniam G., Webb W. W., Wu X. L., Xu C.. Science[J], 1998, 281: 1653—1656 [6]Bhawalkar J. D., He G. S., Prasad P. N.. Rep. Prog. Phys.[J], 1996, 59: 1041—1070 [7]Liu Z. Q., Fang Q., Cao D. X., Wang D., Xu G. B.. Org. Lett.[J], 2004, 6: 2933—2936 [8]Kim O. K., Lee K. S., Woo H. Y., Kim K. S., Guang S. H., Swiatkiewicz J., He J. S., Prasad P. N.. Chem. Mater.[J], 2000, 12: 284—286 [9]Cao D. X., Fang Q., Wang D., Liu Z. Q., Xue G., Xu G. B., Yu W. T.. Eur. J. Org. Chem.[J], 2003, 18: 3628—3636 [10]Day P. N., Nguyen K. A., Pachter R.. J. Phys. Chem. B[J], 2005, 109(5): 1803 —1814 [11]Werts M. H. V., Gmouh S., Mongin O., Pons T., Mireille B. D.. J. Am. Chem. Soc.[J], 2004, 126(50): 16294—16295 [12]Yang W. J., Kim C. H., Jeong M. Y., Lee S. K., Piao M. J., Jeon S. J., Cho B. R.. Chem. Mater.[J], 2004, 16 (14): 2783—2789 [13]Bartholomew G. P., Rumi M., Pond S. J. K., Perry J. W., Tretiak S., Bazan G. C.. J. Am. Chem. Soc.[J], 2004, 126(37): 11529—11542 [14]Pond S. J. K., Tsutsumi O., Rumi M., Kwon O., Zojer E., Jean-Luc B., Marder S. R., Perry J. W.. J. Am. Chem. Soc.[J], 2004, 126(30): 9291—9306 [15]Yang W. J., Kim D. Y., Kim C. H., Jeong M. Y., Lee S. K., Jeon S. J., Cho B. R.. Org. Lett.[J], 2004, 6(9): 1389—1392 [16]Yoo J., Yang S. K., Jeong M. Y., Ahn H. C., Jeon S. J., Cho B. R.. Org. Lett.[J], 2003, 5(5): 645 —648 [17]Chung S. J., Rumi M., Alain V., Barlow S., Perry J. W., Marder S. R.. J. Am. Chem. Soc.[J], 2005, 127(31): 10844—10845 [18]Huang H., He Q., Lin H., Bai F. L., Sun Z., Li Q. S.. Polym. Adv. Technol.[J], 2004, 15: 84—88 [19]Pond S. J. K., Rumi M., Levin M. D., Parker T. C., Beljonne D., Day M. W., Brédas J. L., Marder S.R., Perry J. W.. J. Phys. Chem. A[J], 2002, 106: 11470—11480 [20]HUANG Chi-Bao(黄池宝), REN An-Xiang(任安祥). Acta Chimica Sinica(化学学报)[J], 2007, 65: 2765—2771 [21]Liu M. S., Jiang X., Liu S., Herguth P., Jen Alex K. Y.. Macromolecules[J], 2002, 35: 3532—3538 [22]Shin D. M., Whitten D. G.. J. Phys. Chem.[J], 1988, 92: 2945—2956 [23]Xu C., Webb W. W.. J. Opt. Soc. Am. B[J], 1996, 13: 481—491 [24]Rumi M., Ehrlich J. E., Heikal A. A., Perry J. W., Barlow S., Hu Z., McCord-Maughon D., Parker T. C., Ro1ckel H., Thayumanavan S., Marder S. R., Beljonne D., Brédas J. L.. J. Am. Chem. Soc.[J], 2000, 122(39): 9500—9510