Issue 39, 2012

A cyanide-bridged trinuclear Fe(ii)–Ru(ii)–Fe(ii) complex with three stable states: synthesis, crystal structures, electronic couplings and magnetic properties

Abstract

Treatment of trans-(Ph-tpy)Ru(PPh3)(CN)2 (Ph-tpy = 4′-phenyl-2,2′:6′,2′′-terpyridine, PPh3 = triphenylphosphine) with 2 equiv of Cp(dppe)Fe(NCCH3)Br (dppe = bis(diphenylphosphino)ethane) in the presence of NH4PF6 produced a trinuclear cyanide-bridged complex, trans-[Cp(dppe)Fe(CN)(Ph-tpy)Ru(PPh3)(CN)Fe(dppe)Cp][PF6]2 (1[PF6]2). Its one-electron oxidation product (1[PF6]3) and two-electron-oxidation product (1[PF6]4) were obtained by oxidation with (Cp)2FePF6 and AgPF6, respectively. Firstly, the crystal structures of the cyanide-bridged complexes with three stable states were fully characterized. The reversible electrochemistry measurement of 12+2+ shows the presence of a long range intervalence interaction between the external iron centres. Both 13+3+ and 14+4+ were considered to be Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis indicated the presence of a moderately strong antiferromagnetic coupling between the two remote Fe(III) ions across the Fe–NC–Ru–CN–Fe array in 14+4+. This proves that the Ru(II)-dicyano complex is a bridging ligand that can transmit electro- and magneto-communication.

Graphical abstract: A cyanide-bridged trinuclear Fe(ii)–Ru(ii)–Fe(ii) complex with three stable states: synthesis, crystal structures, electronic couplings and magnetic properties

Supplementary files

Article information

Article type
Paper
Submitted
17 Mar 2012
Accepted
30 Jul 2012
First published
02 Aug 2012

Dalton Trans., 2012,41, 12163-12169

A cyanide-bridged trinuclear Fe(II)–Ru(II)–Fe(II) complex with three stable states: synthesis, crystal structures, electronic couplings and magnetic properties

X. Ma, S. Hu, C. Tan, Y. Wen, Q. Zhu, C. Shen, T. Sheng and X. Wu, Dalton Trans., 2012, 41, 12163 DOI: 10.1039/C2DT30614J

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