Journal article
Revisiting the Robin-Day Classification through Switchable Electronic States in Multimetallic Vanadium Oxides
Journal of the American Chemical Society
04/14/2026
DOI: 10.1021/jacs.6c00579
PMID: 41978914
Appears in UI Libraries Support Open Access
Abstract
Polyoxovanadate–alkoxide clusters are redox-active molecular oxides offering profound electronic tunability. The oxygen-deficient species [(V6O5)(μ6-O)(μ2-OCH3)12] is an ideal platform for probing the multisite localization and delocalization of redox states. Here, we introduce the redox topology modulation which is governed by the position of the central μ6-O oxygen and ligand coordination at the oxygen-deficient site as the mechanism controlling the stability of different electromers. The noncoordinated cluster exhibits a localized, Robin–Day class I/II hybrid ground state, featuring a V(III) center at the vacancy defect. We demonstrate computationally that ligand-field tuning inverts this behavior; coordination of a strong donor destabilizes the localized topology, stabilizing an electromer with all V(IV) topology as the new ground state. Time-dependent density functional theory calculations show that photoexcitation of species where centers are V(IV) triggers photoinduced intervalence charge transfer regenerating a valence-trapped class II excited state. This work establishes the redox topology modulation as a rational design principle for molecular switches, where the fundamental electronic topology can be toggled by chemical stimulus and/or by light. Furthermore, our results suggest that the Robin–Day classification should be revised and extended for multicenter systems, where valence behavior is better understood as excitation-specific rather than molecular-specific.
Details
- Title: Subtitle
- Revisiting the Robin-Day Classification through Switchable Electronic States in Multimetallic Vanadium Oxides
- Creators
- Nghia Le - University of Iowa, ChemistryPere Miró - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society
- DOI
- 10.1021/jacs.6c00579
- PMID
- 41978914
- NLM abbreviation
- J Am Chem Soc
- ISSN
- 0002-7863
- eISSN
- 1520-5126
- Publisher
- American Chemmical Society
- Grant note
- Division of Chemistry: 2145657
N.L. and P.M. thank the National Science Foundation for the support (NSF CAREER CHE-2145657 and CHE-2438306). All density functional theory calculations supporting this project were performed on high-performance computing systems at the University of Iowa.
- Language
- English
- Electronic publication date
- 04/14/2026
- Academic Unit
- Chemistry
- Record Identifier
- 9985153528202771
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