Electronic Structure and Circular Dichroism of Tris(bipyridyl) Metal Complexes within Density Functional Theory

被引：38

作者：

Fan, Jing ^{[1
]}

Autschbach, Jochen ^{[2
]}

Ziegler, Tom ^{[1
]}

机构：

[1] Univ Calgary, Dept Chem, Calgary, AB T2N 1N4, Canada

[2] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA

来源：

INORGANIC CHEMISTRY | 2010年 / 49卷 / 04期

基金：

美国国家科学基金会;

关键词：

DIFFERENTIAL-OVERLAP CALCULATIONS; OPTICAL ROTATORY POWER; COORDINATION-COMPOUNDS; CONJUGATED LIGANDS; RESPONSE THEORY; ELECTROLUMINESCENT DEVICES; PHENANTHROLINE COMPLEXES; ABSOLUTE CONFIGURATIONS; CHIROPTICAL PROPERTIES; NANOCRYSTALLINE TIO2;

D O I：

10.1021/ic9011586

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Time-dependent density functional theory (TD-DFT) has been employed to calculate the electronic circular dichroism (CD) spectra of tris-bidentate iron group complexes [M(L-L)(3)](2+) (M = Fe, Ru, Os; L-L = 2,2'-bipyridine). The simulated CD spectra are compared with the experiment, and reasonably good agreement is obtained, In this study, much effort has been made to interpret the exciton CD arising from the long-axis-polarized pi -> pi* excitations in the ligands of the complexes. Metal-ligand orbital interactions as well as the origin of the optical activity of the exciton transitions have been elucidated in connection with the detailed analysis of the TD-DFT results within a general model that is applicable to similar chiral compounds.

引用

页码：1355 / 1362

页数：8

共 69 条

[1] Theoretical characterization of the lowest triplet excited states of the tris-(1,4,5,8-tetraazaphenanthrene) ruthenium dication complex [J].