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Updated: Jul 11, 2025

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
Structure and Electronic Properties of Large Oligomeric Heterometallic 3d/CeIV Polyoxometalates
Olivier Oms1, Nishith Maity2, Jérôme Marrot1
1Institut Lavoisier de Versailles (ILV), UMR 8180, Université Paris-Saclay, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France.
Abstract:
Merging the rich chemistry of Ce(IV) polyoxometalates (POMs) with that of 3d polyanions remains a challenge due to the strong competition between these highly oxophilic lanthanide cations and 3d metallic ions for coordination to lacunary molecular metal oxides. We report herein the characterization of an unprecedented water stable hexameric CeIV/CoII POM (CeCo) made of two {(SiW9)2Ce6} units connected to a {(SiW10)2Co6(PO4)2} core. In addition, the pentameric CeIV/NiII compound CeNi, where two {PW9Ni3W} and a {PW10Ni2} fragments are grafted on a {(PW9)2Ce6} moiety, has been obtained. Magnetic studies of CeNi revealed ferromagnetic interactions between the NiII centers constituting the {Ni3PW10} fragments, in agreement with the geometry of such a trinuclear cluster. Related insoluble barium salts of CeCo and CeNi were also prepared, allowing their solid-state electrochemical investigations and showing in particular that in CeCo, both the cobalt, cerium, and silicotungstate moieties are electroactive. Finally, photophysical studies demonstrate the formation of long-lived reduced POMs photosensitized by [Ru(bpy)3]2+, suggesting that CeCo and CeNi could be used as efficient reservoirs of reduction equivalents for photocatalytic reactions.
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