Self-assembly of a trigonal bipyramidal architecture with stabilisation of iron in three spin states

Abstract

Self-assembly and characterisation of a supramolecular trigonal bipyramidal iron cage containing an [Fe^III(μ₂-F)₆(Fe^II)₃]³⁺ star motif at its core is reported. The complex can be formed in a one step reaction using an heterotopic ligand that supports site-specific incorporation of iron in three distinct electronic configurations: low-spin Fe^II, high-spin Fe^II and high-spin Fe^III, with iron(II) tetrafluoroborate as the source of the bridging fluorides. Formation of a μ₂-F bridged mixed-valence Fe^II–Fe^III star is unprecedented. The peripheral high-spin Fe^II centres of the mixed-valence tetranuclear star incorporated in the iron cage are highly anisotropic and engage in F-mediated antiferromagnetic exchange with the central Fe^III ion.