具有多金属氧酸盐配体的方形与四面体铁簇合物

Square versus tetrahedral iron clusters with polyoxometalate ligands.

作者信息

Pichon Céline, Dolbecq Anne, Mialane Pierre, Marrot Jérôme, Rivière Eric, Sécheresse Francis

机构信息

Institut Lavoisier, UMR 8180, Université de Versailles Saint-Quentin-en Yvelines, 45 Avenue des Etats-Unis, 78035, Versailles Cedex, France.

出版信息

Dalton Trans. 2008 Jan 7(1):71-6. doi: 10.1039/b714377j.

DOI:10.1039/b714377j

PMID:18399231

Abstract

Two new insoluble transition metal substituted phosphotungstates, (C2N2H10)11[{(B-alpha-PW9O34)Fe3(OH)3}4(PO4)4Fe].38H2O(1) and K4(C2N2H10)12[(alpha-PW10Fe2O39)4].30H2O(2), have been isolated by the hydrothermal reaction of [A-alpha-PW9O34]9-, Fe(III) ions and ethylenediamine. Compound 1 has a tetrahedral symmetry and contains a Fe13 core built from the assembly of four Fe(III) trisubstituted [B-alpha-PW9O34]9- anions around a central disordered iron ion via four phosphato ligands. The anion in 2 can be described as a square of disubstituted [PW10O37]9- anions linked by Fe(III)-O-Fe(III) bridges. Magnetic measurements performed on 1 and 2 have shown the occurrence of antiferromagnetic interactions between the iron ions and have allowed the coupling constants between the magnetic centers to be determined.

摘要

通过[A-α-PW9O34]9-、铁(III)离子和乙二胺的水热反应，分离出了两种新的不溶性过渡金属取代的磷钨酸盐，(C2N2H10)11[{(B-α-PW9O34)Fe3(OH)3}4(PO4)4Fe].38H2O(1)和K4(C2N2H10)12[(α-PW10Fe2O39)4].30H2O(2)。化合物1具有四面体对称性，包含一个Fe13核，该核由四个Fe(III)三取代的[B-α-PW9O34]9-阴离子通过四个磷酸根配体围绕一个中心无序铁离子组装而成。2中的阴离子可描述为由Fe(III)-O-Fe(III)桥连接的二取代[PW10O37]9-阴离子的正方形。对1和2进行的磁性测量表明铁离子之间存在反铁磁相互作用，并确定了磁中心之间的耦合常数。