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

AuthorsBarrios, L. A.; Bartual-Murgui, Carlos; Peyrecave-Lleixà, Eugènia; Le Guennic, Boris; Teat, Simon J.; Roubeau, Olivier; Aromí, Guillem
Issue Date2016
PublisherAmerican Chemical Society
CitationInorganic Chemistry 55(9): 4110-4116 (2016)
AbstractWe show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L′)](ClO) 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(HL1)(Cl-tpy)](ClO)·CHO (1), [Fe(HL3)(Me3bpp)](ClO)·CHO (2), [Fe(HL1)(2bbp)](ClO)·3CHO (3). Structural studies demonstrate that 1 is in the low-spin (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(HL1)(2bbp)](ClO) (3a), through a single-crystal-to-single-crystal transformation. This guest extrusion process is accompanied by a spin switch, from HS to LS.
Identifiersdoi: 10.1021/acs.inorgchem.5b02058
e-issn: 1520-510X
issn: 0020-1669
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