Homoleptic versus heteroleptic formation of mononuclear Fe(II) complexes with tris-imine ligands

Abstract

We show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L′)](ClO4)2 complexes from pairs of chelating tris-imine 3bpp, tpy, or 2bbp ligands. New synthetic avenues for spin crossover research become thus available, here illustrated with three new heteroleptic compounds with differing magnetic behaviors: [Fe(H4L1)(Cl-tpy)](ClO4)2·C3H6O (1), [Fe(H2L3)- (Me3bpp)](ClO4)2·C3H6O (2), [Fe(H4L1)(2bbp)](ClO4)2· 3C3H6O (3). Structural studies demonstrate that 1 is in the lowspin (LS) state up to 350 K, while complexes 2 and 3 are, by contrast, in the high-spin (HS) state down to 2 K, as corroborated through magnetic susceptibility measurements. Upon exposure to the atmosphere, the latter exhibits the release of three molecules of acetone per complex, turning into the solvent-free analogue [Fe(H4L1)(2bbp)](ClO4)2 (3a), through a singlecrystal- to-single-crystal transformation. This guest extrusion process is accompanied by a spin switch, from HS to LS.