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Updated: Oct 10, 2026
Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Equatorial thiolate ligand effects in polynuclear dysprosium metallocene single-molecule magnets
Dan Liu1, Abdullah A Al-Kahtani2, Liviu Chibotaru3
1School of Science, Changchun Institute of Technology Changchun 130012 P. R. China.
Abstract:
Thiolate ligands provide a valuable platform on which to study how soft, polarizable donor atoms affect local magnetic anisotropy and exchange coupling in polynuclear dysprosium single-molecule magnets (SMMs). Here, we report the synthesis of the naphthylthiolate-bridged dysprosium metallocene dimer [(CpMe)2Dy(μ-SNaph)]2 (Dy2S2) and trimer [(CpMe)2Dy(μ-SNaph)]3 (Dy3S3) (CpMe = C5H4Me), obtained selectively through temperature-dependent crystallization from the same reaction mixture. The two compounds enable direct comparison of the influence of nuclearity on magnetic behaviour while retaining closely related dysprosium coordination environments. Both compounds exhibit zero-field SMM behaviour with similar effective barriers to magnetic relaxation of 61 and 64 cm-1, respectively, together with significant Raman relaxation at lower temperatures. Ab initio calculations reveal strongly axial ground Kramers doublets with comparable crystal field splittings for all Dy3+ centres. The calculations accurately reproduce the experimental magnetic susceptibility and isothermal magnetization, revealing that increased nuclearity strengthens the antiferromagnetic exchange without significantly perturbing the local magnetic anisotropy.
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