Spin-crossover behavior of bis[dihydrobis(4-methylpyrazol-1-yl-borate)]-(2,2′-bipyridine)iron and analogous complexes in the bulk and in thin films: Elucidating the influence of π–π-interactions on the type of spin transition**Dedicated to Prof Philipp Gütlich on the occasion of his 85th anniversary.

Abstract

The new complex [Fe(H2B(4-CH3-pz)2)2(bipy)] (1, pz = pyrazole, bipy = 2,2′-bipyridine) is synthesized and investigated by temperature-dependent magnetic measurements, Mößbauer, electronic absorption and vibrational spectroscopy as well as single crystal x-ray diffraction. In the crystal structure of 1 the complexes are pairwise linked to dimers by intermolecular π–π interactions between their bipyridine ligands, with a shortest intradimer distance between two neighboring pyridine rings of 3.575 Å. Analysis of the crystal structures of related iron(II) bis(dihydrobis(pyrazoyl)borate) complexes reveals that most of them contain similar dimers, and that at short π–π intra-dimer distances the complexes are locked in the high-spin state whereas at long distances complete thermal spin crossover (SCO) is observed. Compound 1 with an intermediate π–π intra-dimer distance shows incomplete SCO in the bulk but complete SCO in vacuum-deposited thin films where intermolecular interactions are absent. The implications of this remarkable structure-property relationship are discussed.