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：余中[1] 王玉雪 韩家才 韩晶[2] YU Zhong;WANG Yu‑Xue;HAN Jia‑Cai;HAN Jing(Department of Applied Chemistry,Xi′an University of Technology,Xi′an 710054,China;Department of Materials Physics and Chemistry,Xi′an University of Technology,Xi′an 710048,China)

机构地区：[1]西安理工大学应用化学系,西安710054 [2]西安理工大学材料物理与化学系,西安710048

出　　处：《无机化学学报》2023年第5期947-958,共12页Chinese Journal of Inorganic Chemistry

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(No.12JK0614);陕西省科技厅重点研发计划(No.2018PT-27,2018GY-125,2019NY-201);西安理工大学校基金(No.109-400210929)资助。

摘　　要：首次合成了一个含氰基二噻吩乙烯闭环体化合物(L_(c)),用IR、^(1)H NMR及X射线单晶衍射研究其结构,表明它是一对R,R和S,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(CF_(3)SO_(3))自组装合成了配合物1,并用元素分析、IR、^(1)H 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。A new cyano-equipped dithienylethene in closed-ring form(L_(c))was first isolated and structurally characterized by IR,^(1)H 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(CF_(3)SO_(3))resulting in complex 1.Its structure was characterized by elemental analysis,IR,^(1)H NMR,and ESI-MS.Complex 1 demonstrated reversible photochromism in the solid state with the sameλ_(max)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.CCDC:1953340,L_(c).

关 键 词：二噻吩乙烯 闭环异构体 光致变色 单晶结构 配合物 

分 类 号：O614.122[理学—无机化学]