Journal
INORGANIC CHEMISTRY
Volume 62, Issue 46, Pages 18856-18863Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.3c02078
Keywords
-
Categories
Ask authors/readers for more resources
In this study, an unprecedented water stable hexameric Ce-IV/Co-II POM (Ce12Co6) and a pentameric Ce-IV/Ni-II compound Ce6Ni8 were successfully synthesized and characterized. The magnetic studies confirmed ferromagnetic interactions between the Ni-II centers in Ce6Ni8, and solid-state electrochemical investigations showed that both the cobalt, cerium, and silicotungstate moieties in Ce12Co6 are electroactive. Photophysical studies demonstrated the formation of long-lived reduced POMs photosensitized by [Ru(bpy)(3)](2+), indicating that Ce12Co6 and Ce6Ni8 could be used as efficient reservoirs of reduction equivalents for photocatalytic reactions.
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 Ce-IV/Co-II POM (Ce12Co6) made of two {(SiW9)(2)Ce-6} units connected to a {(SiW10)(2)Co-6(PO4)(2)} core. In addition, the pentameric Ce-IV/Ni-II compound Ce6Ni8, where two {PW9Ni3W} and a {PW10Ni2} fragments are grafted on a {(PW9)(2)Ce-6} moiety, has been obtained. Magnetic studies of Ce6Ni8 revealed ferromagnetic interactions between the Ni-II 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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available