Tuning of the [Cu3(μ-O)]4+/5+ redox couple:: Spectroscopic evidence charge delocalization in the mixed-valent [Cu3(μ-O)]5+ species

被引：45

作者：

Rivera-Carrillo, Marlyn ^{[1
]}

Chakraborty, Indranil ^{[1
]}

Mezei, Gellert ^{[1
]}

Webster, Richard D. ^{[2
]}

Raptis, Raphael G. ^{[1
]}

机构：

[1] Univ Puerto Rico, Dept Chem, San Juan, PR 00931 USA

[2] Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, Singapore 637371, Singapore

来源：

INORGANIC CHEMISTRY | 2008年 / 47卷 / 17期

关键词：

D O I：

10.1021/ic800531y

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Trinuclear Cu-II-complexes of formula [Cu-3(II)(mu(3)-E)(mu-4-R-pz)(3)X-3](+/- n), E = O and OH; R = H, Cl, Br, CH(O) and NO2; X = Cl, NCS, CH3COO, and py, have been synthesized and characterized and the effect of substitution of terminal ligands, as well as 4-R-groups, in the one-electron oxidation process has been investigated by cyclic voltammetry. In situ UV-vis-NIR spectroelectrochemical characterization of the mixed valence Cu-3(7+)-complex [Cu-3(mu(3)-O)(mu-pz)(3)Cl-3](-) revealed an intervalence charge transfer band at 9550 cm(-1) (E = 2600 cm(-1) M-1), whose analysis identifies this species as a delocalized, Robin-Day class-III system, with an electronic coupling factor, H-ab, of 4775 cm(-1).

引用

页码：7644 / 7650

页数：7

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