Magnetic characterization study reveals distinct magnetic orderings in molybdenum chloride compounds, highlighting how structural motifs and cation substitution dictate magnetic behavior.
The evolution of magnetic properties in molybdenum chloride systems caused by structural motif changes was investigated by magnetic property measurements and DFT calculations. In ξ-MoCl5, characterized by the presence of molybdenum dimers, the formation of ferromagnetic (FM) order is observed at T1 = 12.4 K and its additional transformation at T2 = 2.6 K. The influence of the electronic structure on the FM state was studied by substituting Nb5+ and Re5+ for Mo5+. Replacing half the Mo5+(4d1) cations with Re5+(5d2) leads to the formation of a ferrimagnetically ordered state below TNRe1 = 3.8 K and its additional transformation below TNRe2 = 2.6 K in Re0.5Mo0.5Cl5. In contrast, introducing Nb5+(4d0) suppresses a long-range order formation in Nb0.5Mo0.5Cl5. The PCl4MoCl6 compound containing isolated MoCl6– octahedral anions exhibits transition to a long-range ferrimagnetic order below TNPCl4 = 4.2 K.
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Vorobyova et al. (2026) studied this question.
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