Organometallic-polyoxometalate hybrid compounds: Metallosalen compounds modified by Keggin type polyoxometalates

被引：124

作者：

Bar-Nahum, I

Cohen, H

Neumann, R ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel

[2] Weizmann Inst Sci, Div Chem Sci, IL-76100 Rehovot, Israel

来源：

INORGANIC CHEMISTRY | 2003年 / 42卷 / 11期

关键词：

D O I：

10.1021/ic034095s

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Hybrid compounds with two functional centers consisting of a metallosalen moiety (M-salen; M = Mn, Co, Ni, and Pd) connected by an alkylene bridging group to a lacunary Keggin type polyoxometalate were synthesized and characterized. In these metallosalen-polyoxometalate compounds (M-salen-POM) it was shown by the use of a combination of UV-vis, H-1 NMR, EPR, XPS, and cyclic voltammetry measurements that the polyoxometalate exerts a significant intramolecular electronic effect on the metallosalen moiety leading to formation of an oxidized metallosalen moiety. For the Mn-salen-POM, the metallosalen center is best described as a metal-salen cation radical species; that is, a localized "hole" is formed on the salen ligand. For the other M-salen-POM compounds, the metallosalen moiety can be described as a hybrid of a metal-salen cation radical species and an oxidized metal-salen species, that is, a delocalized "hole" is formed at the metallosalen center. It is proposed that these oxidized metallosalen centers are best characterized as stabilized charge transfer (metallosalen donor-polyoxometalate acceptor) complexes despite the relatively large distance between the two functional centers.

引用

页码：3677 / 3684

页数：8

共 53 条

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