Effect of magnetic fields on the methyl rotation in a paramagnetic cobalt(ii) complex. Quasielastic neutron scattering studies

Stavretis, Shelby E.; Mamontov, Eugene; Moseley, Duncan H.; Cheng, Yongqiang; Daemen, Luke L.; Ramirez-Cuesta, Anibal J.; Xue, Zi -Ling

doi:10.1039/c8cp01660g

Title: Effect of magnetic fields on the methyl rotation in a paramagnetic cobalt(ii) complex. Quasielastic neutron scattering studies

Journal Article · Fri Jul 27 00:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c8cp01660g· OSTI ID:1484105

Stavretis, Shelby E. ^[1];

^[2]; Moseley, Duncan H. ^[1];

^[2]; Daemen, Luke L. ^[2];

^[2];

^[1]

Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Molecular dynamics is a fundamental property of metal complexes. These dynamic processes, especially for paramagnetic complexes under external magnetic fields, are in general not well understood. Quasielastic neutron scattering (QENS) in 0–4 T magnetic fields has been used to study the dynamics of Co(acac)₂(D₂O)₂ (1-d₄, acac = acetylacetonate). At 80–100 K, rotation of the methyl groups on the acac ligands is the dominant dynamical process. This rotation is slowed down by the magnetic field increase. Rotation times at 80 K are 5.6(3) × 10^–10 s at 0 T and 2.04(10) × 10^–9 s at 4 T. The QENS studies suggest that methyl groups in these paramagnetic Co(II) molecules do not behave as isolated units, which is consistent with results from earlier magnetic susceptibility studies indicating the presence of intermolecular interactions. DFT calculations show that unpaired electron spin density in 1 is dispersed to the atoms of both acac and H₂O ligands. Methyl torsions in 1-d₄ have also been observed at 5–100 K in inelastic neutron spectroscopy (INS). In conclusion, the QENS and INS results here help understand the dynamics of the compound in the solid state.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1484105

Alternate ID(s):: OSTI ID: 1463037

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 32; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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Title: Effect of magnetic fields on the methyl rotation in a paramagnetic cobalt(ii) complex. Quasielastic neutron scattering studies

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