1 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet2 Pharmaceutical Technology and Engineering, Department of Pharmacy, Faculty of Health and Medical Sciences, Københavns Universitet3 Department of Chemistry, Faculty of Science, Københavns Universitet4 Institut Max Von Laue Paul Langevin5 The Royal Danish Academy of Fine Arts, Schools of Architecture, Design and Conservation6 Laboratoire National des Champs Magnétiques Intenses, CNRS7 Department of Chemistry, Faculty of Science, Københavns Universitet8 Administration, Department of Chemistry, Faculty of Science, Københavns Universitet9 Pharmaceutical Technology and Engineering, Department of Pharmacy, Faculty of Health and Medical Sciences, Københavns Universitet
magnetic and spectroscopic characterization of discrete, linearly bridged [Mn<sup>III<sub>2</sub></sup>(μ-F)F<sub>4</sub>(Me<sub>3</sub>tacn)<sub>2</sub>(PF<sub>6</sub>)
The nature of the magnetic interaction through fluoride in a simple, dinuclear manganese(III) complex (1), bridged by a single fluoride ion in a perfectly linear fashion, is established by experiment and density functional theory. The magnitude of the antiferromagnetic exchange interaction and the manganese(III) zero-field-splitting parameters are unambiguously determined by inelastic neutron scattering to yield J = 33.0(2) cm(-1) (Ĥ = JŜ1·Ŝ2 Hamiltonian definition) and single-ion D = -4.0(1) cm(-1). Additionally, high-field, high-frequency electron paramagnetic resonance and magnetic measurements support the parameter values and resolve |E| ≈ 0.04 cm(-1). The exchange coupling constant (J) is 1 order of magnitude smaller than that found in comparable systems with linear oxide bridging but comparable to typical magnitudes through cyanide, thus underlining the potential of fluoride complexes as promising building blocks for novel magnetic systems.
Inorganic Chemistry, 2014, Vol 53, Issue 10, p. 5013-5019