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Updated: Aug 12, 2026
09:56
High Resolution Physical Characterization of Single Metallic Nanoparticles
Published on: June 28, 2019
Gas phase fragmentation provides structural insights into mixed-ligand polyoxovanadate alkoxides
Solita Wilson1, Ashley Johnson2, Liam Ryan1
1James Tarpo Jr. and Margaret Tarpo Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA. jlaskin@purdue.edu.
Physical Chemistry Chemical Physics : PCCP
|August 11, 2026
Summary
Investigating polyoxovanadate-alkoxides (POV-alkoxides) for batteries, this study used mass spectrometry to analyze mixed-ligand shells. Cationic clusters showed ligand segregation, unlike anionic ones, revealing charge-dependent fragmentation patterns.
Area of Science:
- * Inorganic Chemistry
- * Materials Science
- * Electrochemistry
Background:
- * Atomically precise clusters are crucial for designing advanced materials like non-aqueous redox flow batteries.
- * Tailoring ligand shells in these clusters often results in mixed-ligand species, complicating structural analysis.
- * Polyoxovanadate-alkoxides (POV-alkoxides) with Lindqvist cores are promising for energy storage but require detailed structural characterization.
Purpose of the Study:
- * To investigate the structural properties of polyoxovanadate-alkoxides (POV-alkoxides) with mixed ethoxy (EtO) and ethoxyethyl (EOE) ligand shells.
- * To understand the fragmentation behavior of these mixed-ligand POV-alkoxides using collision-induced dissociation (CID) mass spectrometry.
- * To establish a framework for elucidating the structures of POV-alkoxides with complex ligand shells.
Main Methods:
- * Employed collision-energy-resolved collision-induced dissociation (CID) mass spectrometry in both positive and negative ion modes.
- * Analyzed fragmentation patterns of polyoxovanadate-alkoxides (POV-alkoxides) with Lindqvist cores and mixed EtO/EOE ligand shells.
- * Compared the stability and fragmentation pathways of cationic and anionic POV-alkoxide species.
Main Results:
- * Cationic POV-alkoxide species exhibited lower stability and a bias toward ethoxyethyl (EOE) ligand incorporation in fragments, suggesting ligand segregation.
- * Anionic POV-alkoxide species required higher CID energies, showed near-statistical ligand incorporation, and produced numerous fragments, complicating analysis.
- * Charge and ligand composition significantly influence fragmentation pathways in POV-alkoxides.
Conclusions:
- * Collision-induced dissociation (CID) mass spectrometry is a powerful tool for analyzing mixed-ligand POV-alkoxides without prior separation.
- * Fragmentation pathways are dependent on the charge state and ligand composition of POV-alkoxides.
- * The study provides a foundational framework for the structural elucidation of complex POV-alkoxide clusters in energy storage applications.
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