title: How does a coordinated radical ligand affect the spin crossover properties in an octahedral iron(II) complex?
abstract: 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.
authors.affiliation: Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger Strasse 54, 67663 Kaiserslautern (Germany) http://www.chemie.uni-kl.de/fachrichtungen/ac/krueger/
authors.forename: Markus
authors.initials: M
authors.lastname: Schmitz
authors.forename: Manuel
authors.initials: M
authors.lastname: Seibel
authors.forename: Harald
authors.initials: H
authors.lastname: Kelm
authors.forename: Serhiy
authors.initials: S
authors.lastname: Demeshko
authors.forename: Franc
authors.initials: F
authors.lastname: Meyer
authors.forename: Hans-Jörg
authors.initials: HJ
authors.lastname: Krüger
keywords: iron(II) complexes; magnetic properties; redox chemistry; spin crossover; π-radical ligands