Journal article
Nucleation Roadmap of Reduced Polyoxovanadate-Alkoxide Clusters
Inorganic chemistry, Vol.64(8), pp.3790-3795
03/03/2025
DOI: 10.1021/acs.inorgchem.4c04759
PMCID: PMC11881037
PMID: 39973095
Appears in UI Libraries Support Open Access
Abstract
Polyoxovanadate-alkoxides are a growing family of earth-abundant first-row transition metal polynuclear species highly promising for their tunable redox properties. The speciation and nucleation chemical space of these species is divided into two groups: 1) fully oxidized V(V) monomeric precursors that aggregate into Lindqvist-type clusters and 2) reduced V(IV) precursors forming cyclic structures. The nucleation of cyclic polyoxovanadate-alkoxides with varying alkyl chain lengths, the impact of the presence of templating anions, and their subsequent evolution to the Lindqvist-type congener were studied by using density functional theory. The evolution of cyclic polyoxovanadate-alkoxides to oxygen-vacant cluster structures was found to be endergonic, in agreement with previous experimental work. Moreover, the reactivity with traces of water in alcohol solvents was confirmed to be the main thermodynamic driving force toward the formation of the mixed-valent Lindqvist-type polyoxovanadate species.
Details
- Title: Subtitle
- Nucleation Roadmap of Reduced Polyoxovanadate-Alkoxide Clusters
- Creators
- S Genevieve Duggan - University of South DakotaS M Gulam Rabbani - University of South DakotaPere Miró - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.64(8), pp.3790-3795
- DOI
- 10.1021/acs.inorgchem.4c04759
- PMID
- 39973095
- PMCID
- PMC11881037
- NLM abbreviation
- Inorg Chem
- ISSN
- 1520-510X
- eISSN
- 1520-510X
- Publisher
- American Chemical Society
- Grant note
- Division of Chemistry: NSF CAREER CHE-2145657, CHE-2438306 National Science Foundation: OAC-1626516 University of South Dakota Chemistry Department - NSF MRI
S.G.D. and P.M. thank the National Science Foundation for the support (NSF CAREER CHE-2145657 and CHE-2438306). S.M.G.R. thanks the University of South Dakota Chemistry Department for graduate support. All density functional theory calculations supporting this project were performed on high-performance computing systems at the University of South Dakota, funded by NSF MRI award OAC-1626516.
- Language
- English
- Electronic publication date
- 02/19/2025
- Date published
- 03/03/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984792364002771
Metrics
3 Record Views