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.
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