Theoretical study of the electronic structures and spectroscopic properties of [(4'-XC≡Ctrpy)PtCl]^+ (trpy=2,2':6',2"-terpyridine;X=H,Me and Ph)

作     者：WANG Xin,BAI FuQuan,ZHOU Xin,LIU Tao & ZHANG HongXing State Key Laboratory of Theoretical and Computational Chemistry,Institute of Theoretical Chemistry,Jilin University,Changchun 130023,China 

作者机构：State Key Laboratory of Theoretical and Computational Chemistry Institute of Theoretical Chemistry Jilin University Changchun China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2009年第52卷第12期

页      面：2226-2236页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：Supported by the National Natural Science Foundation of China (Grant No. 20573042) China Postdoctoral Science Foundation (Grant No. 20080440149) 

主　　题：platinum(Ⅱ) complexes TD-DFT absorption spectra charge transfer luminescence 

摘      要：The electronic structures and spectroscopic properties of [(4 -XC≡Ctrpy)PtCl]+(trpy = 2,2 :6 ,2″-terpyridine; X = H (1),methyl (Me) (2),and phenyl (Ph) (3) were studied by the ab initio method. The structures at the ground and excited state were optimized at the B3LYP and CIS levels,respectively. The absorption and emission spectra in the dichloromethane solution were obtained by using the TD-DFT (B3LYP) method associated with the PCM model. The molecular orbital energy of the HOMOs of 1-3 with the d(Pt),p(Cl),π(trpy),and π(XC≡C) character is sensitive to the substituents on the acetylide ligand,but that of the trpy-based LUMOs with the π*(trpy) character varies slightly. The lowest lying emission at 503 nm for 1 is mainly attributed to the 3ILCT perturbed by the 3MLCT and 3LLCT transitions,but that at 535 nm for 2,and that at 558 nm for 3 are mainly attributed to the 3LLCT perturbed by the 3ILCT and 3MLCT transitions. The different electron-donating ability of H,Me,and Ph is responsible for the differences in emission character. Moreover,the calculation results show that the phosphorescent color can be turned by adjusting the substituents. Both the lowest energy absorption and emission of 1―3 are red-shifted in the order of 123,consistent with the electron-donating of HMePh.