High-Frequency Electron-Spin-Resonance Study of the Octanuclear Ferric Wheel CsFe8

TY - JOUR

T1 - High-Frequency Electron-Spin-Resonance Study of the Octanuclear Ferric Wheel CsFe8

AU - Dreiser, J.

AU - Waldmann, O.

AU - Carver, G.

AU - Dobe, C.

AU - Gudel, H.-U.

AU - Weihe, Høgni

AU - Barra, A.-L.

PY - 2010/10/4

Y1 - 2010/10/4

N2 - High-frequency (f = 190 GHz) electron paramagnetic resonance (EPR) at magnetic fields up to 12 T and Q-band (f = 34.1 GHz) EPR were performed on single crystals of the molecular wheel CsFe8. In this molecule, eight FeIII ions, which are coupled by nearest-neighbor antiferromagnetic (AF) Heisenberg exchange interactions, form a nearly perfect ring. The angle-dependent EPR data allow for the accurate determination of the spin Hamiltonian parameters of the lowest spin multiplets with S ≤ 4. Furthermore, the data can be well reproduced by a dimer model with a uniaxial anisotropy term, with only two free parameters J and D. A fit to the dimer model yields J = -15(2) cm-1 and D = -0.3940(8) cm-1. A rhombic anisotropy term is found to be negligibly small, E = 0.000(2) cm-1. The results are in excellent agreement with previous inelastic neutron scattering and high-field torque measurements. They confirm that the CsFe8 molecule is an excellent experimental model of an AF Heisenberg ring. These findings are also important within the scope of further investigations on this molecule such as the exploration of recently observed magnetoelastic instabilities.

AB - High-frequency (f = 190 GHz) electron paramagnetic resonance (EPR) at magnetic fields up to 12 T and Q-band (f = 34.1 GHz) EPR were performed on single crystals of the molecular wheel CsFe8. In this molecule, eight FeIII ions, which are coupled by nearest-neighbor antiferromagnetic (AF) Heisenberg exchange interactions, form a nearly perfect ring. The angle-dependent EPR data allow for the accurate determination of the spin Hamiltonian parameters of the lowest spin multiplets with S ≤ 4. Furthermore, the data can be well reproduced by a dimer model with a uniaxial anisotropy term, with only two free parameters J and D. A fit to the dimer model yields J = -15(2) cm-1 and D = -0.3940(8) cm-1. A rhombic anisotropy term is found to be negligibly small, E = 0.000(2) cm-1. The results are in excellent agreement with previous inelastic neutron scattering and high-field torque measurements. They confirm that the CsFe8 molecule is an excellent experimental model of an AF Heisenberg ring. These findings are also important within the scope of further investigations on this molecule such as the exploration of recently observed magnetoelastic instabilities.

M3 - Journal article

SN - 0020-1669

VL - 49

SP - 8729

EP - 8735

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 19

ER -