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Updated: Jan 14, 2026
Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Investigating How the Charge and Distance of Equatorial Ligands Impact the Structural, Magnetic, and Electronic
Jarrod R Thomas1, Emily A Murray-Nobbs1, Richard A Mole2
1School of Chemistry, The University of New South Wales (UNSW), Kensington, Sydney 2052, Australia.
Abstract:
Due to the recent success of [Dy(Tp2-py)F(THF)2](PF6) (Tp2-py = hydrotris(3-(2'-pyridyl)-pyrazol-1-yl)borate) as a single-ion magnet (SIM), which increased the effective anisotropic energy of the [Dy(Tp2-py)F(X)2]+ moiety to Ueff = 661(6) cm-1, we report the systematic study of replacing the equatorial solvent ligands within this moiety with 4,4'-bipyridine, MeOH, TMSO, DMSO, DMF, and H2O, along with the heteroleptic solvent ligand complex of MeOH/THF. The minute changes in the structural properties, i.e., the Dy-F and Dy-solvent coordination bond distances, and the use of solvent molecules capable of hydrogen bonding result in a striking difference in the magnetic and electronic properties. Through a combination of magnetometry and ab initio calculations we have found that the [Dy(Tp2-py)F(X)2]+ moiety produces pure (mJ ≈ 0.99| ± 15/2⟩) and highly axially anisotropic (gz ≈ 19.8) ground states due to the presence of the hard terminally coordinated fluoride ion, however the solvent molecules coordinated equatorially along with the isolation of the [Dy(Tp2-py)F(X)2]+ cation play important roles in the slow magnetic relaxation behavior. While the THF adduct still reigns supreme, the use of these alternative solvent ligands results in zero-field SIM behavior for all analogues, presenting Orbach-type magnetic relaxation with energy barriers between 342(11) ≤ Ueff ≤ 661(6) cm-1.
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