Structural and physical characterization of tetranuclear [Mn3IIMnIV] and [Mn2IIMn2III] valence-isomer manganese complexes

被引：30

作者：

Zaleski, Curtis M. ^{[3
]}

Weng, Tsu-Chen ^{[1
]}

Dendrinou-Samara, Catherine ^{[2
]}

Alexiou, Maria ^{[2
]}

Kanakaraki, Paraskevi ^{[2
]}

Hsieh, Wen-Yuan ^{[1
]}

Kampf, Jeff ^{[1
]}

Penner-Hahn, James E. ^{[1
]}

Pecoraro, Vincent L. ^{[1
]}

Kessissoglou, Dimitris P. ^{[2
]}

机构：

[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48107 USA

[2] Aristotle Univ Thessaloniki, Dept Chem, Thessaloniki 54124, Greece

[3] Shippensburg Univ, Dept Chem, Shippensburg, PA 17257 USA

来源：

INORGANIC CHEMISTRY | 2008年 / 47卷 / 14期

关键词：

D O I：

10.1021/ic702109c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Two tetranuclear Mn complexes with an average Mn oxidation state of +2.5 have been prepared. These valence isomers have been characterized by a combination of X-ray crystallography, X-ray absorption spectroscopy, and magnetic susceptibility. The (Mn3MnIV)-Mn-II tetramer has the Mn ions arranged in a distorted tetrahedron, with an S = 6 ground spin state, dominated by ferromagnetic exchange among the manganese ions. The (Mn2Mn2III)-Mn-II tetramer also has a distorted tetrahedral arrangement of Mn ions but shows magnetic behavior, suggesting that it is a single-molecule magnet. The X-ray absorption near-edge structure (XANES) spectra for the two complexes are similar, suggesting that, while Mn XANES has sufficient sensitivity to distinguish between trinuclear valence isomers (Alexiou et al. Inorg. Chem. 2003, 42, 2185), similar distinctions are difficult for tetranuclear complexes such as that found in the photosynthetic oxygen-evolving complex.

引用

页码：6127 / 6136

页数：10

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