一个含联吡啶的螯合二噻吩乙烯新配体合成、结构和光致变色性质研究  

A new chelating dithienylethene ligand containing bipyridyl:syntheses,structures and photochromism

作　　者：余中[1] 陈怡璇 杨键 韩晶[2] YU Zhong;CHEN Yixuan;YANG Jian;HAN Jing(Faculty of Sciences,Xi’an University of Technology,Xi’an 710054,China;Faculty of Materials Science and Engineering,Xi’an University of Technology,Xi’an 710048,China)

机构地区：[1]西安理工大学理学院,陕西西安710054 [2]西安理工大学材料科学与工程学院,陕西西安710048

出　　处：《西安理工大学学报》2025年第1期134-140,共7页Journal of Xi'an University of Technology

基　　金：教育部留学回国人员启动基金;陕西省教育厅科学研究计划项目(12JK0614);陕西省科技厅重点研发计划项目(2018PT-27,2018GY-125,2019NY-201);西安理工大学校基金项目(109-400210929)。

摘　　要：为提高二噻吩乙烯光致闭环反应的转化率,延长光致开环反应的激发波长从而实现信号的低能读取,首次设计并合成了一个具有联吡啶基的新螯合配体1,2-双-[2′-甲基-5′-(5″-联吡啶)-3′-噻吩]全氟环戊烯(BM-5-BP-3-TP)及其闭环体closed-BM-5-BP-3-TP,将其作为配体与金属离子组装成金属有机框架(MOFs)以实现调节配体光致变色的目的。借助红外光谱、核磁共振氢谱、质谱和元素分析对中间产物3-溴-2-甲基-5-(5′-联吡啶)噻吩(BM-5-BPT)和BM-5-BP-3-TP进行了结构表征,用紫外-可见光谱法研究了BM-5-BP-3-TP在液相的光致变色性质及其对不同极性溶剂的依赖性,其闭环体在甲醇中的最大吸收波长为612 nm;光反应动力学研究表明,闭环反应为零级反应,而开环反应为一级反应。此外,BM-5-BP-3-TP在PMMA薄膜相和晶体相均具有可逆的光致变色性质,闭环体最大吸收波长分别为608 nm和614 nm,且在PMMA薄膜中具有优异的耐疲劳性质。In order to improve the conversion of photo-induced cyclization of dithienylethenes and extend the excitation wavelength of photo-induced conversion for low-energy read-out,a new chelating ligand containing bipyridyl 1,2-bis-[2′-methyl-5′-(5″-bipyridyl)-3′-thienyl]perfluorocyclopentene(BM-5-BP-3-TP)as well as its closed-ring isomer(closed-BM-5-BP-3-TP)were designed and synthesized firstly for realization of further modulation their photochromism by self-assembly of the ligand with metal ions into Metal-Organic Frameworks.The structures of intermediate 3-bromo-2-methyl-5-(5′-bipyridyl)thiophene(BM-5-BPT)and BM-5-BP-3-TP were characterized by IR,1 HNMR,MS and EA.The photochromism and polarity dependence of BM-5-BP-3-TP in varied solvent were investigated by UV-Vis spectroscopy.The maximum absorption wavelength of the closed-ring isomer in MeOH is 612 nm.The photo-isomerization kinetics indicated that the photo-cyclization belongs to zeroth-order process whereas the photo-conversion follows a first-order process.BM-5-BP-3-TP showed reversible photochromism in both PMMA films and crystalline phase withλmax at 608 nm and 614 nm,respectively.It exhibited excellent fatigue resistance in PMMA films.

关 键 词：二噻吩乙烯 螯合配体 光致变色 光反应动力学 晶体相 光疲劳 

分 类 号：O626[理学—有机化学]