Bis(pyrazolato) Bridged Diiron Complexes: Ferromagnetic Coupling in a Mixed-Valent HS-FeII/LS-FeIII Dinuclear Complex
By Wong, Joanne W. L.; Hua, Shao-An; Demeshko, Serhiy; Dechert, Sebastian; Ye, Shengfa; Meyer, Franc
Published in European Journal of Inorganic Chemistry
2020
Abstract
Using a new bis(tridentate) compartmental pyrazolate-centered ligand HL, the bis(pyrazolato)-bridged diiron complex [L2FeII2][OTf]2 (1) and its singly oxidized mixed-valent congener [L2FeIIFeIII][OTf]3 (2) have been synthesized and structurally characterized. While 1 features two HS-FeII ions coordinated to two cis-axial pyridine moieties in a highly distorted octahedral environment, the metal ions in 2 are coordinated by the ligand strand in a trans-axial configuration. Very different Fe–N bond lengths and distinctly different coordination polyhedra are associated with pronounced valence localization in the case of 2. The electronic structures and magnetic properties of 1 and 2 have been further investigated by Mössbauer spectroscopy and variable temperature magnetic susceptibility measurements. In the case of 1, weak antiferromagnetic coupling is observed between the two HS-FeII ions (J = –0.6 cm–1), while the HS-FeII and LS-FeIII ions in 2 are ferromagnetically coupled (J = +5.2 cm–1) to give an ST = 5/2 ground state with significant zero-field splitting (DFe(II) = 2.3 cm–1). The findings are rationalized with the help of DFT computations.