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Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films
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Nucleation Roadmap of Reduced Polyoxovanadate-Alkoxide Clusters
S Genevieve Duggan1,2, S M Gulam Rabbani2, Pere Miró1,2
1Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States.
Inorganic Chemistry
|February 20, 2025
Summary
Polyoxovanadate-alkoxides, promising for redox properties, were studied. Water reactivity drives the formation of mixed-valent Lindqvist-type polyoxovanadate species from cyclic precursors.
Area of Science:
- Inorganic Chemistry
- Materials Science
Background:
- Polyoxovanadate-alkoxides are earth-abundant transition metal clusters with tunable redox properties.
- Their speciation involves V(V) precursors forming Lindqvist-type clusters and V(IV) precursors forming cyclic structures.
Purpose of the Study:
- Investigate the nucleation of cyclic polyoxovanadate-alkoxides.
- Determine the impact of alkyl chain length and templating anions on nucleation.
- Study the evolution of cyclic structures to Lindqvist-type congeners.
Main Methods:
- Density functional theory (DFT) calculations were employed.
- Thermodynamic analysis of cluster evolution was performed.
Main Results:
- The evolution of cyclic polyoxovanadate-alkoxides to oxygen-vacant clusters is endergonic.
- Reactivity with trace water in alcohol solvents is the primary thermodynamic driver.
- Formation of mixed-valent Lindqvist-type polyoxovanadate species is favored.
Conclusions:
- Water plays a crucial role in the transformation of polyoxovanadate-alkoxides.
- DFT provides insights into the speciation and nucleation pathways.
- Understanding these pathways is key to designing novel vanadium-based materials.
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