TUNING OF THROUGH-BOND ELECTRONIC COUPLING BY DONOR AND ACCEPTOR SUBSTITUTIONS IN THE [(NH3)5RU-1,4-DICYANOBENZENE-RU(NH3)5]5+ COMPLEX

被引：10

作者：

JOACHIM, C

机构：

[1] Molecular Electronics Group, CEMES-LOE, 31055 Toulouse Cedex, 29, rue Jeanne Marvig -

来源：

CHEMICAL PHYSICS LETTERS | 1991年 / 185卷 / 5-6期

关键词：

D O I：

10.1016/0009-2614(91)80261-U

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Through-ligand electronic coupling in the [(NH3)5Ru(III)-1,4-dicyanobenzene-Ru(II)(NH3)5]5+ complex is calculated depending on the donor or acceptor grafted on the benzene. The coupling strength is first discussed, showing that through-dicyanobutadiene is larger than through-1,4-dicyanobenzene coupling. With this ligand, the largest electronic coupling is reached with a full 4NO2 substitution on the benzene. Coupling through an asymmetric 2NO22NH2-substituted benzene is one order of magnitude lower. This large difference is interpreted using the number and position of the active ligand molecular orbitals relative to the druthenium orbital.

引用

页码：569 / 575

页数：7

共 31 条

[1] LIMITING FORMS OF THE TUNNELING MATRIX ELEMENT IN THE LONG-DISTANCE BRIDGE MEDIATED ELECTRON-TRANSFER PROBLEM [J].