Magnetic Properties and New Structural Classification of Molybdenum Phosphates Containing Mo(V)
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Abstract
A combined theoretical and experimental study of molybdenum phosphates containing Mo(V) either as purely Mo(V) or as mixed-valent Mo(V)/Mo(VI) and Mo(IV)/Mo(V) is performed. This investigation, based on a structural classification of molybdenum phosphates, derived from that proposed by Costentin et al., allows a detailed discussion of both the valence of the different Mo sites as well as the different coupling mechanisms for the unpaired electron of the Mo(V) octahedra. Either direct Mo−Mo or indirect interaction through the shared oxygen atoms can lead to magnetic moments per Mo(V) lower than expected. It is shown that although the PO4 tetrahedra do not effectively couple the unpaired electrons of the different Mo(V)O6 octahedra, they play an important role in determining the magnetic properties of these solids by influencing the internal geometry of the MoO6 octahedra.
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