Achieving T-Type Photochromism through Generating Copper(I)Metallacyclopentadiene Biradical  

作　　者：Xu Zhang Jin-Yun Wang Liang-Jin Xu Xu-Yuan Jin Xin Yang Li-Yi Zhang Zhong-Ning Chen 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou,Fujian 350002 [2]Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou,Fujian 350108 [3]University of Chinese Academy of Sciences,Beijing 100039

出　　处：《CCS Chemistry》2022年第12期3832-3841,共10页中国化学会会刊（英文）

基　　金：This work was supported by the National Natural Science Foundation of China(grant nos.92061202,22175181,and 21531008);the Fujian Science and Technology Project(grant no.2020L3022);the Strategic Priority Research Program of the Chinese Academy of Sciences(grant no.XDB20000000).

摘　　要：Photochromism due to organometallic ring-closure through C−C linkage has never been attained.In this work,we report a preliminary approach to achieve T-type photochromism by creating a metallacyclopentadiene biradical under light irradiation.A class of CuPt2 phenylacetylide compounds was prepared with distinguished photochromic recyclability and durability,which involved the formation of thermally sensitive copper(I)-butadienyl,five-membered ring through copper(I)-participated ring-closure.Upon UV light irradiation,the metallacyclopentadiene with copper(I)center chelated by 1,3-butadiene-1,4-diyl biradical was generated through photochemical C-C linkage of two face-to-face oriented ethynyl units in close proximity,giving rise to a drastic change in UV-vis absorption spectrum.When UV light irradiation was ceased,decoloration occurred through thermal cycloreversion,which endowed the photochromic CuPt2 complexes with self-recovery characteristics.Electron paramagnetic resonance(EPR)spectral study confirmed a biradical feature of a ring-closed isomer.The thermal decoloration half-lives at ambient temperature were regulated from seconds to hours by increasing F substituents in phenylethynyl ligands.

关 键 词：heteronuclear complex PHOTOCHROMISM BIRADICAL organometallic ring-closure thermal cycloreversion 

分 类 号：O62[理学—有机化学]