Journal article
Structure, Properties, and Reactivity of Polyoxocationic Zirconium and Hafnium Clusters: A Computational Investigation
Inorganic chemistry, Vol.62(13), pp.5081-5087
04/03/2023
DOI: 10.1021/acs.inorgchem.2c04142
PMID: 36951309
Abstract
Tetravalent zirconium and hafnium molecular metal oxides clusters are key building blocks of many metal-organic frameworks; however, the chemical space to form all possible MOF nodes is vast, containing many potential new clusters. Our computational study provides a complete picture of the structure, properties, and reactivity of two tetrameric zirconium and hafnium [M4(mu 2-r/2:r/2-O2)x(mu 2-OH)8-2x(H2O)16]8+ polycationic clusters. The electronic structure of the studied species has characteristic polyoxometalate oxygen-based and metal-based bands in the valence region. The energetics for the evolution of pure metal clusters into mixed-metal clusters revealed that only the incorporation of zirconium into hafnium clusters is thermodynamically favorable. We confirmed that the incorporation of up to four peroxide ligands is thermodynamically favorable; however, the experimental absence of rich peroxide species with three or more peroxides is attributed to their thermal degradation. The mechanism for peroxide incorporation involves the partial dissociation of the cluster rather than complete dissociation.
Details
- Title: Subtitle
- Structure, Properties, and Reactivity of Polyoxocationic Zirconium and Hafnium Clusters: A Computational Investigation
- Creators
- Rameswar Bhattacharjee - University of South DakotaEthan T. Hare - University of South DakotaPere Miro - University of South Dakota
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.62(13), pp.5081-5087
- Publisher
- Amer Chemical Soc
- DOI
- 10.1021/acs.inorgchem.2c04142
- PMID
- 36951309
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Number of pages
- 7
- Grant note
- OAC-1626516 / National Science Foundation through an MRI Award
- Language
- English
- Date published
- 04/03/2023
- Academic Unit
- Chemistry
- Record Identifier
- 9984618648802771
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