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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/185205
Allosteric Spin Crossover Induced by Ligand-Based Molecular Alloying
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he spin crossover (SCO) phenomenon represents a source of multistability at the molecular level, and dilution into a nonactive host was originally key to understand its cooperative nature and the parameters governing it in the solid state. Here, we devise a molecular alloying approach in which all components are SCO-active, but with significantly different characteristic temperatures. Thus, the molecular material [Fe(Mebpp)2](ClO4)2 (2) has been doped with increasing amounts of the ligand Me2bpp (Mebpp and Me2bpp = methyl- and bis-methyl-substituted bis-pyrazolylpyridine ligands), yielding molecular alloys with the formula [Fe(Mebpp)2-2x(Me2bpp)2x](ClO4)2 (4x; 0.05 < x < 0.5). The effect of the composition on the SCO process is studied through single-crystal X-ray diffraction (SCXRD), magnetometry, and differential scanning calorimetry (DSC). While the attenuation of intermolecular interactions is shown to have a strong effect on the SCO cooperativity, the spin conversion was found to occur at intermediate temperatures and in one sole step for all components of the alloys, thus unveiling an unprecedented allosteric SCO process. This effect provides in turn a means of tuning the SCO temperature within a range of 42 K.
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BARTUAL-MURGUI, Carlos, et al. Allosteric Spin Crossover Induced by Ligand-Based Molecular Alloying. Inorganic Chemistry. 2020. Vol. 59, num. 17, pags. 12132-12142. ISSN 0020-1669. [consulted: 7 of October of 2026]. Available at: https://hdl.handle.net/2445/185205