Magnetic Interactions through Fluoride: Magnetic and Spectroscopic Characterization of Discrete, Linearly Bridged [Mn-2(III)(mu-F)F-4(Me(3)tacn)(2)](PF6)

作者：Pedersen Kasper S; Sigrist Marc; Weihe Hogni; Bond Andrew D; Thuesen Christian Aa; Simonsen Kim P; Birk Torben; Mutka Hannu; Barra Anne Laure; Bendix Jesper^*

来源：Inorganic Chemistry, 2014, 53(10): 5013-5019.

DOI：10.1021/ic500049w

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) ((H) over cap = J (S-1) over cap.(S-2) over cap 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 vertical bar E vertical bar approximate to 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.

• 出版日期2014-5-19