具有多步氧化还原行为的氰基桥连铁（II,III）立方体

Cyanide-bridged iron(II,III) cube with multistepped redox behavior.

作者信息

Nihei Masayuki, Ui Mayumi, Hoshino Norihisa, Oshio Hiroki

机构信息

Graduate School of Pure and Applied Sciences, Department of Chemistry, University of Tsukuba, Tennodai 1-1-1, Tsukuba 305-8571, Japan.

出版信息

Inorg Chem. 2008 Jul 21;47(14):6106-8. doi: 10.1021/ic7024582. Epub 2008 Jun 19.

DOI:10.1021/ic7024582

PMID:18563896

Abstract

A building unit of Prussian blue was isolated as a cyanide-bridged iron cube of [Fe(II)4Fe(III)4(CN)12(tp)8] x 12 DMF x 2 Et2O x 4 H2O [tp(-) = hydrotris(pyrazolyl)borate]. A cyclic voltammogram showed quasi-reversible four-stepped redox waves, which correspond to [Fe(III)4Fe(II)4]/Fe(III)5Fe(II)3, Fe(III)5Fe(II)3/Fe(III)6Fe(II)2, Fe(III)6Fe(II)2/Fe(III)7Fe(II)1, and Fe(III)7Fe(II)1/Fe(III)8 processes. Controlled potential absorption spectral measurements revealed two intervalence charge-transfer bands at 816 and 1000 nm, which were assigned to charge transfers from Fe(II) ions to adjacent and remote Fe(III) ions, respectively, in the cube.

摘要

普鲁士蓝的一个结构单元被分离为[Fe(II)4Fe(III)4(CN)12(tp)8] x 12 DMF x 2 Et2O x 4 H2O（tp(-)=氢三(吡唑基)硼酸根）的氰基桥连铁立方体。循环伏安图显示了准可逆的四步氧化还原波，其分别对应于[Fe(III)4Fe(II)4]/Fe(III)5Fe(II)3、Fe(III)5Fe(II)3/Fe(III)6Fe(II)2、Fe(III)6Fe(II)2/Fe(III)7Fe(II)1以及Fe(III)7Fe(II)1/Fe(III)8过程。控制电位吸收光谱测量在816和1000 nm处揭示了两个价间电荷转移带，它们分别被归属于立方体中从Fe(II)离子到相邻和远程Fe(III)离子的电荷转移。