Electron paramagnetic resonance and UV-Vis absorption study of trans-(1,4,8,11-tetraazacyclotetradecane)chromium(III) complexes

被引：15

作者：

Ueki, S ^{[1
]}

Yamauchi, J ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Human & Environm Studies, Kyoto 6068501, Japan

来源：

INORGANICA CHIMICA ACTA | 2002年 / 338卷

关键词：

chromium(Ill) complexes; cyclam complexes; covalency;

D O I：

10.1016/S0020-1693(02)00899-X

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The electronic structures of the trans -[Cr-III(cyclam)X-2]"(+) (cyclam = 1,4,8,11-tetraazacyclotetradecane, X = Cl-, OH-, and H2O) were investigated. The spin quartet excited states of these complexes were assigned on the basis of a Gaussian analysis of UV-Vis absorption spectra. The spin Hamiltonian parameters of the ground states, especially the zero-field splittings, were determined from the randomly oriented frozen solution electron paramagnetic resonance spectra. The calculated zero-field splitting parameters determined from the second-order spin-orbit couplings with the nearest excited quartet states were found to deviate from those observed experimentally. The deviations were found to reflect the bond covalency of the axial ligators. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：13 / 18

页数：6

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