The influence of a coordinated π-radical on the spin crossover properties of an octahedral iron(II) complex was investigated by preparing and isolating the iron(II) complex containing the tetradentate N,N'-dimethyl-2,11-diaza[3.3](2,6)pyridinophane and the radical anion of N,N'-diphenyl-acenaphtene-1,2-diimine as ligands. This spin crossover complex was obtained by a reduction of the corresponding low-spin iron(II) complex with the neutral diimine ligand, demonstrating that the reduction of the strong π-acceptor ligand is accompanied by a decrease in the ligand field strength. Characterization of the iron(II) radical complex by structural, magnetochemical, and spectroscopic methods revealed that spin crossover equilibrium occurs above 240 K between an S=1/2 ground state and an S=3/2 excited spin state. The possible origins of the fast spin interconversion observed for this complex are discussed.
Keywords: iron(II) complexes; magnetic properties; redox chemistry; spin crossover; π-radical ligands.
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.