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Updated: Aug 17, 2026

Thermochemical Studies of Ni(II) and Zn(II) Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Single-molecule magnets: high-field electron paramagnetic resonance evaluation of the single-ion zero-field
En-Che Yang1, Cem Kirman, Jon Lawrence
1Department of Chemistry and Biochemistry, University of California at San Diego, La Jolla, California 92093-0358, USA.
Abstract:
High-field electron paramagnetic resonance spectra were collected at several frequencies for a single crystal of [Zn3.91Ni0.09(hmp)4(dmb)4Cl4] (1), where dmb is 3,3-dimethyl-1-butanol and hmp- is the monoanion of 2-hydroxymethylpyridine. This crystal is isostructural to [Ni4(hmp)4(dmb)4Cl4] (2), which has been characterized to be a single-molecule magnet (SMM) with fast quantum tunneling of its magnetization (QTM). The single Ni(II) ion zero-field-splitting (zfs) parameters Di [= -5.30(5) cm(-1)] and Ei [= +/-1.20(2) cm(-1)] in the doped complex 1 were evaluated by rotation of a crystal in three planes. The easy-axes of magnetization associated with the single-ion zfs interactions were also found to be tilted 15 degrees away from the crystallographic c direction. This inclination provides a possible explanation for the fast QTM observed for complex 2. The single-ion zfs parameters are then related to the zfs parameters for the Ni4 molecule by irreducible tensor methods to give D = -0.69 cm(-1) for the S = 4 ground state of the SMM, where the axial zfs interaction is given by DS(Z)2.
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