通过重卤素配体效应增强氰基配位的铬(II)和铬(III)配合物的磁各向异性。

Enhancing the magnetic anisotropy of cyano-ligated chromium(II) and chromium(III) complexes via heavy halide ligand effects.

机构信息

Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.

出版信息

Inorg Chem. 2010 Jun 7;49(11):4738-40. doi: 10.1021/ic1002995.

PMID:20443564

Abstract

A method of increasing the axial zero-field splitting parameter for transition metal complexes of utility in the assembly of magnetic clusters is demonstrated through the use of heavy atoms as auxiliary ligands. The octahedral complexes Cr(dmpe)(2)(CN)X (dmpe = 1,2-bis(dimethylphosphino)ethane, X = Cl, Br, I) and Cr(dmpe)(2)(CN)X (X = Cl, I) are synthesized and structurally characterized. Variable-field magnetization measurements show the magnitude of D for these complexes to increase significantly as the halide ligand varies from chloride to iodide, ranging from 0.11 cm(-1) for Cr(dmpe)(2)(CN)Cl to 6.26 cm(-1) for Cr(dmpe)(2)(CN)I.

摘要

通过使用重原子作为辅助配体，展示了一种提高过渡金属配合物在组装磁团簇中轴向零场分裂参数的方法。合成并结构表征了八面体配合物Cr(dmpe)(2)(CN)X（dmpe=1,2-双（二甲基膦基）乙烷，X=Cl、Br、I）和 Cr(dmpe)(2)(CN)X（X=Cl、I）。变场磁化率测量表明，这些配合物的 D 值随着卤化物配体从氯到碘的变化而显著增加，范围从Cr(dmpe)(2)(CN)Cl的 0.11 cm(-1)到 Cr(dmpe)(2)(CN)I 的 6.26 cm(-1)。