Density Functional Theory Study on the First Hyperpolarizabilities of Mono-and Bimetal Ir(Ⅰ)/Rh(Ⅰ) 2,2?-Bidipyrrins Complexes

被引：0

作者：

荆丽雪 ^{[1
]}

王丽 ^{[1
]}

陈珍珍 ^{[1
]}

陈赫 ^{[1
]}

仇永清 ^{[1
]}

机构：

[1] Institute of Functional Material Chemistry, Faculty of Chemistry,Northeast Normal University

来源：

结构化学 | 2017年 / 36卷 / 06期

基金：

中国国家自然科学基金;

关键词：

Ir(Ⅰ)/Rh(Ⅰ) complexes; DFT; second-order NLO response; charge-transfer;

D O I：

暂无

中图分类号：

O641.4 [络合物化学（配位化学）];

学科分类号：

070304 ; 081704 ;

摘要：

Metal complexes with excellent nonlinear optical(NLO) properties have attracted considerable attention. The geometry structure, electronic spectra and NLO properties of 2,2?-bidipyrrins(L) and mono-and bimetal Ir(I)/Rh(I)–L complexes have been investigated by density functional theory method. Our calculations revealed that L with planar configuration shows the largest first hyperpolarizability value, which is 2.2 to 5.5 times larger than that of others. It is attributed to the single direction of intramolecular charge transfer. When metal ions were embedded in ligands, the first hyperpolarizability values of mono-and bimetal Ir/Rh(I)–L complexes were smaller than that of L, and that of bimetal Ir/Rh(I)–L complexes were smaller than the corresponding monometallic Ir/Rh(I)–L. This is caused by the intramolecular charge transfer from multiple directions as well as the amount of charge transfer. On the other hand, on increasing the number of metal ions, the charge transfer in the opposite direction cancels each other more obviously. Our work would provide some theoretical reference for the second-order NLO responses of mono-and bimetal complexes.

引用

页码：877 / 885

页数：9