IrR(CO)(PH_3)_2(mnt)配合物的基态和激发态结构及光谱性质的理论研究  

Theoretical Studies on the Ground- and Excited-State Structures and the Spectroscopic Properties of IrR(CO)(PH_3)_2(mnt) Complexes

作　　者：吴玉辉[1] 周欣[1] 王嵩[1] 白福全[1] 张建坡[1] 张红星[1] 孙家锺[1] 

机构地区：[1]吉林大学理论化学研究所理论化学计算国家重点实验室,长春130023

出　　处：《化学学报》2009年第1期33-38,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.20573042;20333050)资助项目

摘　　要：应用MP2和CIS方法分别优化了IrR(CO)(PH3)2(mnt)[mnt=maleonitriledithiolate;R=H(1),CH3(2),Br(3)]系列配合物的基态和激发态几何结构.使用TD-DFT方法计算了配合物的吸收和发射光谱.计算结果表明:配合物1～3在430,435及439nm处的最低能吸收均为ILCT/LLCT/MLCT混合跃迁性质,它们的最低能磷光发射和吸收性质相似,发射波长则红移至760,770和800nm.配合物2与1的几何结构、光谱性质都很接近,而配合物3中,由于溴的引入使其基态和激发态几何构型及前线分子轨道成分与1和2有很大不同,进而对其光谱及跃迁性质产生了影响.MP2 and CIS methods were used to optimize the ground- and excited-state structures of IrR（CO）（PH3）2（mnt） complexes [mnt=maleonitriledithiolate; R=H （1）, Me （2）, and Br （3）]. The absorption and emission spectra were calculated using a TD-DFT method. The calculated results indicated that the lowest-energy absorptions of 1 43 at 430, 435 and 439 nm were all the admixture of the ILCT/LLCT/MLCT transitions. The emissions were red-shifted to 760, 770 and 800 nm, the origins of which are similar to those of the lowest-energy absorptions. The structure and spectroscopic properties of 2 and 1 are close with each other, but the introduction of Br for 3 changes the ground- and excited-state geometries and the compositions of frontier orbitals, which affects the emission spectra and transition characters.

关 键 词：Ir配合物 激发态 溶剂化效应 TD—DFT 

分 类 号：O641.4[理学—物理化学]