期刊
COORDINATION CHEMISTRY REVIEWS
卷 254, 期 13-14, 页码 1448-1456出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2009.12.035
关键词
Dithiolato and dithiolene ligands; Diimine ligands; DFT technique; Excited states; Fukui; NICS; Stacking interactions
This review is focused on theoretical aspects of mixed diimine-dithiolate complexes by means of OFT and TD-DFT methods. Thus, the geometry, the character of charge-transfer transitions and excited states in a series of M(diimine)(dithiolate), where M = Ni, Pd and Pt, is examined by OFT and ID-OFT techniques combined with polarized continuum model. The theoretical calculations reveal not only the role of the ligands - namely diimine and dithiolato and their substituents - but also the role of the metal in the excited triplet and singlet states and as a consequence in the properties of these complexes (electronic and photophysics) and their potential use as photosensitizers, NLO materials, light energy conversion materials and biological agents. The calculated energies of the lowest triplet and singlet state in all these complexes are in good agreement with absorption spectra and luminescence studies where they are available. The contribution of the metal in the chemical and photophysics properties of this class of compounds is also demonstrated by two indices derived by OFT techniques: NICS (for chemical) and Fukui functions (for chemical and photophysical properties). The former acts as a meter of the delocalization of these molecules whereas the latter identifies the reactive centres of the molecule. All the theoretical results are in accordance with the experimental ones-geometrical structures, absorption, luminescence and H-1 NMR spectra as well as products of given reactions, indicating the applicability of the DFT and TD-DFT techniques in examining the properties of metal coordinated complexes especially in a series of the same class of compounds. (C) 2010 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据