一个闭环二噻吩乙烯及其Ag(Ⅰ)配合物的合成、结构和光致变色性质
A closed-ring dithienylethene and its Ag(Ⅰ) complex: Syntheses, structures, and reversible photochromism
作者单位E-mail
余中 西安理工大学应用化学系, 西安 710054  
王玉雪 西安理工大学材料物理与化学系, 西安 710048  
韩家才 西安理工大学材料物理与化学系, 西安 710048  
韩晶 西安理工大学材料物理与化学系, 西安 710048 hanj@xaut.edu.cn 
摘要: 首次合成了一个含氰基二噻吩乙烯闭环体化合物(Lc),用IR、1H NMR及X射线单晶衍射研究其结构,表明它是一对R,RS,S对映异构体组成的消旋混合物,证实了光化学顺旋环化反应中己三烯结构转变为环己二烯结构。紫外可见光谱研究表明其在THF溶液和固相均具有可逆的光致变色性质,可见区最大吸收波长为607 nm。光异构化动力学研究表明开环反应为一级反应,而闭环反应为0级反应。将其进一步用作配体与Ag (CF3SO3)自组装合成了配合物1,并用元素分析、IR、1H NMR及电喷雾质谱进行结构表征。1在固相具有可逆的光致变色性质,但与开环配体组装的配合物不同,由于刚性的闭环配体结构限制了2个噻吩环的自由旋转,银离子与闭环配体配位未能修饰配体的吸收波长,1的可见区最大吸收波长与配体相同。与闭环配体相比,1的光异构化反应速度更快,这和循环伏安法测得其具有比配体更小的带隙结果一致。
关键词: 二噻吩乙烯  闭环异构体  光致变色  单晶结构  配合物
基金项目: 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(No.12JK0614)、陕西省科技厅重点研发计划(No.2018PT-27,2018GY-125,2019NY-201)和西安理工大学校基金(No.109-400210929)资助。
Abstract: A new cyano-equipped dithienylethene in closed-ring form (Lc) was first isolated and structurally characterized by IR, 1H NMR, and X-ray single-crystal diffraction. It showed an interesting racemic mixture of R,R and S,S enantiomer pairs evidencing the structural transformation from 1,3,5-hexatriene to cyclohexadiene in the photochemical conrotatory cyclization. Followed UV-Vis spectral investigations exhibited its reversible photochromism in both THF solution and solid state with the maximum absorption wavelength of 607 nm observed in the visible band. The photo-isomerization kinetics of the compound indicated a first-order process for photo-reversion and zeroth-order for photo-cyclization. The compound was further used as a ligand to self-assemble with Ag(CF3SO3) resulting in complex 1. Its structure was characterized by elemental analysis, IR, 1H NMR, and ESI-MS. Complex 1 demonstrated reversible photochromism in the solid state with the same λmax as the closed-ring ligand. Unlike the complex derived from the open-ring ligand, Ag(Ⅰ) ions coordination with the closed-ring ligand doesn't modify the absorption due to the restricted free rotation of the thienyl rings in the rigid configuration of the closed-ring ligand. In comparison with the open-ring ligand, 1 displayed a faster photo-isomerization rate corresponding to the smaller band gap determined by cyclic voltammetry.
Keywords: dithienylethene  closed-ring isomer  photochromism  single crystal structure  complex
投稿时间:2022-11-21 修订日期:2023-03-14
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余中,王玉雪,韩家才,韩晶.一个闭环二噻吩乙烯及其Ag(Ⅰ)配合物的合成、结构和光致变色性质[J].无机化学学报,2023,39(5):947-958.
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