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Updated: Sep 27, 2025
Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
Published on: June 7, 2018
Tuning of Cr-Cr Magnetic Exchange through Chalcogenide Linkers in Cr2 Molecular Dimers
Eranga H Gamage1,2, Raquel A Ribeiro2,3, Colin P Harmer1,2
1Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States.
Abstract:
A set of three Cr-dimer compounds, Cr2Q2(en)4X2 (Q: S, Se; X: Br, Cl; en: ethylenediamine), with monoatomic chalcogenide bridges have been synthesized via a single-step solvothermal route. Chalcogenide linkers mediate magnetic exchange between Cr3+ centers, while bidentate ethylenediamine ligands complete the distorted octahedral coordination of Cr centers. Unlike the compounds previously reported, none of the chalcogenide atoms are connected to extra ligands. Magnetic susceptibility studies indicate antiferromagnetic coupling between Cr3+ centers, which are moderate in Cr2Se2(en)4X2 and stronger in Cr2S2(en)4Cl2. Fitting the magnetic data requires a biquadratic exchange term. High-frequency EPR spectra showing characteristic signals due to coupled S = 1 spin states could be interpreted in terms of the "giant spin" Hamiltonian. A fourth compound, Cr2Se8(en)4, has a single diatomic Se bridge connecting the two Cr3+ centers and shows weak ferromagnetic exchange interactions. This work demonstrates the tunability in strength and type of exchange interactions between metal centers by manipulating the interatomic distances and number of bridging chalcogenide linkers.
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