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材料研究学报  2016, Vol. 30 Issue (10): 731-736    DOI: 10.11901/1005.3093.2015.703
  研究论文 本期目录 | 过刊浏览 |
一种偶氮染料及其掺杂薄膜制备、表征及性能*
宋秀美1,2,冯宗财1,2(),丰九英1,2,冯翠娟1,韩冰1
1. 岭南师范学院化学化工学院 湛江 524048
2. 广东高校新材料工程技术开发中心 湛江 524048
Preparation, Characterization and Property of an Azo Dye and Its Doping Film
Xiumei SONG1,2,Zongcai FENG1,2,**(),Jiuying FENG1,2,Cuijuan FENG1,Bing HAN1
1. School of Chemistry and Chemical Engineering, Lingnan Normal University, Zhanjiang 524048, China
2. Development Center for New Materials Engineering & Technology in Universities of Guangdong, Zhanjiang 524048, China;
引用本文:

宋秀美,冯宗财,丰九英,冯翠娟,韩冰. 一种偶氮染料及其掺杂薄膜制备、表征及性能*[J]. 材料研究学报, 2016, 30(10): 731-736.
Xiumei SONG, Zongcai FENG, Jiuying FENG, Cuijuan FENG, Bing HAN. Preparation, Characterization and Property of an Azo Dye and Its Doping Film[J]. Chinese Journal of Materials Research, 2016, 30(10): 731-736.

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摘要: 

合成了偶氮染料3', 5'-二溴-4-(N, N-二甲基)胺基偶氮苯, 利用红外光谱、核磁共振谱、质谱、元素分析和X射线单晶衍射进行结构表征, 通过主客体掺杂法制备偶氮染料聚甲基丙烯酸甲酯掺杂薄膜, 利用紫外-可见光谱、荧光光谱考察偶氮染料溶液态和固态光致异构过程, 热重分析其热稳定性。结果表明: 该染料的晶体分子呈反式构型, 两个苯环与-N=N-基本在同一平面上, 溶液态和固态掺杂薄膜均表现出显著顺反异构性能, 异构转化为一级动力学反应, 反式构型荧光较强, 顺式构型荧光较弱, 250℃以内热稳性良好。

关键词 有机高分子材料偶氮染料光致异构速率常数晶体聚甲基丙烯酸甲酯    
Abstract

An azodye, 3', 5'-dibromo-4-(N, N-dimethyl)aminoazobenzene was synthesized and characterized by IR, NMR, ESI-MS, element analysis and single-crystal X-ray diffraction. Then the azo dyedoped polymethyl methacrylate film was prepared by host-guest doping method. The photoisomerization properties the doped polymethyl methacrylate both in liquid and solidstates were studied by UV-Vis spectrum and fluorescence spectrum. Additionally, the thermostability of azodyewas characterized by TG. The results show that the molecule of azodye crystal exists as trans-isomer, the benzene rings and -N=N- are nearly coplanar. And the azodye both in solvent and film display significant photoisomerization property, with the process describing as the first order kinetics reaction. The fluorescence intensity of the trans-isomer is stronger than that of the cis-isomer. The azodye is stable below 250℃.

Key wordsorganic polymer materials    azodye    photoisomerization    rate constant    crystal    polymethyl methacrylate
收稿日期: 2015-12-04     
基金资助:* 国家自然科学基金51403183和湛江市科技计划2014B01031和2015A02008资助项目
图1  偶氮染料的合成路线及其光致异构过程
图2  偶氮染料单晶的分子结构图
图3  偶氮染料氘代氯仿溶液在λ405的光照射前后一维核磁氢谱图
图4  偶氮染料乙酸乙酯溶液光照各个时刻紫外-可见吸收光谱变化
图5  偶氮染料PMMA掺杂薄膜经405 nm光照射各个时刻紫外-可见吸收光谱变化
图6  偶氮染料在溶剂和PMMA中异构转变一级动力学曲线
图7  偶氮染料在不同极性的溶剂中荧光发射光谱
Solvents Dichlomethane Tetrahydrofuran Acetone Acetonitrile N,N-dimethyl formamide Dimethyl sulfoxide
λem/nm 519 521 526 533 536 541
表1  偶氮染料在不同极性溶剂中的荧光发射光谱
图8  偶氮染料在(a)二氯甲烷和(b)PMMA中光照各个时刻荧光光谱变化
图9  偶氮染料的TG曲线
1 H. R. Wang, F. G. Liu, Y. H. Yang, H. J. Xua, C. C. Peng, S. H. Bo, Z. Zhen, X. H. Liu, L. Qi, Synthesis and optical nonlinear property of NLO chromophores with alkoxy chains of different lengths using 8-hydroxy-1, 1, 7, 7-tetramethyl-formyljulolidine as donor, Dyes Pigments, 112, 42(2015)
2 M. Cigáň, A. Gáplovsky, I. Sigmundová, P. Zahradník, R. D?dic, M. Hromadová, Photostability of D-π-A nonlinear optical chromophores containing a benzothiazolium acceptor, J. Phys. Org. Chem., 24(6), 450(2011)
3 Z. Y. Liu, G. Y. Lu, J. Ma, Tuning the absorption spectra and nonlinear optical properties of D-π-A azobenzene derivatives by changing the dipole moment and conjugation length: a theoretical study, J. Phys. Org. Chem., 24(7), 568(2011)
4 Z . Sefero?lua, H. Ihmelsb, E. Sahinc, Synthesis and photophysical properties of fluorescent arylstyrylimidazo [1, 2-a]pyridine-based donor-acceptor chromophores, Dyes Pigments, 113, 465(2015)
5 M. Q. Wang, X. Y. Ma, J. H. Yu, X. Q. Jia, D. D. Han, T. F. Zhou, J. L. Yang, J. Nie, T. Wang, Aromatic amine-sulfone/sulfoxide conjugated D-π-A-π-D-type dyes in photopolymerization under 405 nm and 455 nm laser beams, Polym. Chem., 6(24), 4424(2015)
6 M. Yamada, M. Kondo, J. Mamiya, Y. L. Yu, M. Kinoshita, C. J. Barrett, T. Ikeda, Photomobile polymer materials: towards light-driven plastic motors, Angew. Chem. Int. Ed., 47(27), 4986(2008)
7 G. C. Yu, C. Y. Han, Z. B. Zhang, J. Z. Chen, X. Z. Yan, B. Zheng, S. Y. Liu, F. H. Huang, Pillar[6]arene-based photoresponsive host-guest complexation, J. Am. Chem. Soc., 134(20), 8711(2012)
8 G. Cornelius, S. Roland, B. Daniel, M. Erik. R, F. Wolfgang, C. Robert, R. Karsten, W. Martin, Structure and excitonic coupling in self-assembled monolayers of azobenzene-functionalized alkanethiols, J. Am. Chem. Soc., 132(6), 1831(2010)
9 X. L. Wang, J. Huang, Y. Y. Zhou, S. Y. Yan, X. C. Weng, X. J. Wu, M. G. Deng, X. Zhou, Conformational switching of G-quadruplex DNA by photoregulation, Angew. Chem. Int. Ed., 49(31), 5305(2010)
10 J. A. Gámez, A. Koslowski, W. Thiel, Enhanced E/Z photoisomerisation in 2-aminoazobenzene, RSC Adv., 4(4), 1886(2014)
11 A. A. Beharry, O. Sadovski, G. A. Woolley, Azobenzene photoswitching without ultraviolet light, J. Am. Chem. Soc., 133(49), 19684(2011)
12 T. Cusati, G. Granucci, M. Persico, Photodynamics and time-resolved fluorescence of azobenzene in solution: a mixed quantum-classical simulation, J. Am. Chem. Soc., 133(13), 5109(2011)
13 G. D. Costanzo, S. Ledesma, I. Mondragon, S. Goyanes, Stable solutions of multiwalled carbon nanotubes using an azobenzene dye, J. Phys. Chem. C, 114(34), 14347(2010)
14 SONG Xiumei, FENG Zongcai, WANG Zhaoyang, ZENG Huijuan, LIU Liyan, ZHAN Chaomin, Synthesis, characterization and photochromic properties of D-π-A azobenzene derivatives, J. Funct. Mater., 46(9), 9114(2015)
14 (宋秀美, 冯宗财, 汪朝阳, 曾慧娟, 刘丽燕, 詹超敏, D-π-A型偶氮苯衍生物的合成、表征及其光致变色性能, 功能材料, 46(9), 9114(2015))
15 G. M. Sheldrick, A short history of SHELX. Acta Crystallogr. A, 64(1), 112(2008)
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