Electrochemically‐Switched 2nd Order Non‐Linear Optical Response in an Arylimido‐Polyoxometalate with High Contrast and Cyclability. Issue 5 (27th December 2022)

• Record Type: Journal Article
• Authors: Hood, Bethany R.; de Coene, Yovan; Torre Do Vale Froes, Afonso V.; Jones, Claire F.; Beaujean, Pierre; Liégeois, Vincent; MacMillan, Fraser; Champagne, Benoît; Clays, Koen; Fielden, John
• Is Part Of: Angewandte Chemie international edition. Volume 62:Issue 5(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-27
• Subjects: Donor-Acceptor Systems -- Molecular Devices -- Nonlinear Optics -- Polyoxometalates -- Spectroelectrochemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202215537
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Electrochemically switched 2 nd order non‐linear optical responses have been demonstrated for the first time in polyoxometalates (POMs), with an arylimido‐derivative showing a leading combination of high on/off contrast (94 %), high visible transparency, and cyclability. Spectro‐electrochemical and TD‐DFT studies indicate that the switch‐off results from weakened charge transfer (CT) character of the electronic transitions in the reduced state. This represents the first study of an imido‐POM reduced state, and demonstrates the potential of POM hybrids as electrochemically activated molecular switches. Abstract : Charge transfer transitions in a new arylimido‐polyoxometalate (POM) are turned off by reduction, enabling a high contrast (94 %) electrochemically switched 2 nd order non‐linear optical (NLO) response. The overall combination of on/off contrast, high visible transparency and multicycle stability is leading in switchable 2 nd order NLO chromophores, and shows for the first time the strong potential of POM hybrids as redox‐driven optical switches.