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

Masayuki Nihei; Mayumi Ui; Norihisa Hoshino; Hiroki Oshio

doi:10.1021/ic7024582

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

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

Authors

Masayuki Nihei¹, Mayumi Ui, Norihisa Hoshino, Hiroki Oshio

Affiliation

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

PMID: 18563896
DOI: 10.1021/ic7024582

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](2+), [Fe(III)6Fe(II)2](2+)/[Fe(III)7Fe(II)1](3+), and [Fe(III)7Fe(II)1](3+)/[Fe(III)8](4+) 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.