Structure and Electronic Properties of Large Oligomeric Heterometallic 3d/CeIV Polyoxometalates - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2023

Structure and Electronic Properties of Large Oligomeric Heterometallic 3d/CeIV Polyoxometalates

Résumé

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 (Ce12Co6) made of two {(SiW9)2Ce6} units connected to a {(SiW10)2Co6(PO4)2} core. In addition, the pentameric CeIV/NiII compound Ce6Ni8, where two {PW9Ni3W} and a {PW10Ni2} fragments are grafted on a {(PW9)2Ce6} moiety, has been obtained. Magnetic studies of Ce6Ni8 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 Ce12Co6 and Ce6Ni8 were also prepared, allowing their solid-state electrochemical investigations and showing in particular that in Ce12Co6, 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 Ce12Co6 and Ce6Ni8 could be used as efficient reservoirs of reduction equivalents for photocatalytic reactions.

Domaines

Chimie
Fichier principal
Vignette du fichier
ManuscriptNiCeCo.pdf (947.58 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-04334566 , version 1 (08-01-2024)

Identifiants

Citer

Olivier Oms, Nishith Maity, Jérôme C. Marrot, Jiahao Yu, Eric Rivière, et al.. Structure and Electronic Properties of Large Oligomeric Heterometallic 3d/CeIV Polyoxometalates. Inorganic Chemistry, 2023, 62 (46), pp.18856-18863. ⟨10.1021/acs.inorgchem.3c02078⟩. ⟨hal-04334566⟩
42 Consultations
10 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More