Magnetic interactions through fluoride: magnetic and spectroscopic characterization of discrete, linearly bridged [Mn^III₂(μ-F)F₄(Me₃tacn)₂(PF₆)

TY - JOUR

T1 - Magnetic interactions through fluoride

T2 - magnetic and spectroscopic characterization of discrete, linearly bridged [MnIII2(μ-F)F4(Me3tacn)2(PF6)

AU - Pedersen, Kasper Steen

AU - Sigrist, Marc

AU - Weihe, Høgni

AU - Bond, Andrew

AU - Thuesen, Christian Aagaard

AU - Simonsen, Kim P.

AU - Birk, Torben

AU - Mutka, Hannu

AU - Barra, Anne-Laure

AU - Bendix, Jesper

PY - 2014/5/19

Y1 - 2014/5/19

N2 - 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.

AB - 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.

U2 - 10.1021/ic500049w

DO - 10.1021/ic500049w

M3 - Journal article

C2 - 24601580

SN - 0020-1669

VL - 53

SP - 5013

EP - 5019

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 10

ER -