Electrochemical Switch‐On of Nonlinear Optical Response in a Nitro‐Functionalized Arylimido‐Polyoxometalate
ABSTRACT Electrochemical switch‐on of second‐order non‐linear optical (NLO) responses ( β ) has been demonstrated in a polyoxometalate (POM) based chromophore (POMophore) for the first time. Reduction of the POM in a POM‐imidoaryl‐NO 2 derivative invokes an up to 15‐fold off/on switchable increase in intensity of scattered frequency‐doubled light, and the highest “on” state β yet reported for a redox‐cyclable POMophore. Computational and spectroscopic studies show that in the oxidized state, directionally opposed charge transfer (CT) transitions to POM and ─NO 2 result in a low net β . Upon reduction, the POM becomes a much weaker CT acceptor, resulting in more dipolar imido‐aryl to nitro CT, and thus enhanced NLO response.
Authors
- Hayleigh Kearns (ORCID: https://orcid.org/0000-0003-4526-4651)
- Karen Faulds (ORCID: https://orcid.org/0000-0002-5567-7399)
- Benoı̂t Champagne (ORCID: https://orcid.org/0000-0003-3678-8875)
- Yovan de Coene (ORCID: https://orcid.org/0000-0002-1514-5865)
- John Fielden (ORCID: https://orcid.org/0000-0001-5963-7792)
- Bethany R. Hood
- Koen Clays (ORCID: https://orcid.org/0000-0001-9490-0023)
- Claire F. Jones
Institutions
- University of East Anglia (GB)
- University of Namur (BE)
- University of Strathclyde (GB)
- Lancaster University (GB)
- KU Leuven (BE)
Publication Details
- Journal
- Angewandte Chemie
- Published
- 2026-06-30
- DOI
- https://doi.org/10.1002/ange.4949539
- Primary Topic
- Polyoxometalates: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Lancaster University
- Leverhulme Trust
- University of East Anglia
- Fonds Wetenschappelijk Onderzoek
- Engineering and Physical Sciences Research Council
- Biotechnology and Biological Sciences Research Council