Mixed Valency across Hydrogen Bonds

被引：38

作者：

Goeltz, John C. ^{[1
]}

Kubiak, Clifford P. ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 49期

关键词：

COUPLED ELECTRON-TRANSFER; CHARGE-TRANSFER IVCT; RUTHENIUM CLUSTERS; COMPLEXES; COMMUNICATION; TRANSITIONS; TRINUCLEAR; MOLECULES; DYNAMICS; EXCHANGE;

D O I：

10.1021/ja108841k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An oxo-centered triruthenium cluster with one pyridine-4-carboxylic acid ligand forms a mixed valence monoanionic dicarboxylic acid dimer upon partial reduction. Dimerization is not observed in DMSO or in the deprotonated carboxylate complex. Infrared spectroscopy reveals the mixed valence dimer as a charge localized species, and UV/vis/NIR spectroscopy suggests a large stabilization of the ground state by mixed valency across hydrogen bonds, on the order of 2500 cm(-1), or 7 kcal/mol, relative to the hydrogen bonded but isovalent fully reduced dimer. The stabilization is a combination of hydrogen bonding and electronic coupling.

引用

页码：17390 / 17392

页数：3

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