Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability

Bethany Rose Hood; Yovan de Coene; Afonso Vieira Torre Do Vale Froes; Claire Jones; Pierre Beaujean; Vincent Liegois; Fraser MacMillan; Benoit Champagne; Koen Clays; John Fielden

doi:10.1002/anie.202215537

Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability

Bethany Rose Hood, Yovan de Coene, Afonso Vieira Torre Do Vale Froes, Claire Jones, Pierre Beaujean, Vincent Liegois, Fraser MacMillan, Benoit Champagne, Koen Clays, John Fielden

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Abstract

Electrochemically switched 2nd 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.

Original language	English
Article number	e202215537
Journal	Angewandte Chemie International Edition
Volume	62
Issue number	5
Early online date	30 Nov 2022
DOIs	https://doi.org/10.1002/anie.202215537
Publication status	Published - 26 Jan 2023

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Angew Chem Int Ed - 2022 - Hood - Electrochemically‐Switched 2nd Order Non‐Linear Optical Response in anAccepted author manuscript, 949 KBLicence: CC BY

Enhanced single-crystal X-ray diffraction facilities
Bochmann, M., Fabian, L., Fielden, J., Khimyak, Y. & Wright, J.
Engineering and Physical Sciences Research Council
15/11/18 → 14/11/21
Project: Research
Polyoxometalate-Based Sensitizers for p-Type Dye-Sensitized Solar Cells
Fielden, J.
Engineering and Physical Sciences Research Council
31/12/14 → 29/06/16
Project: Research

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Hood, B. R., de Coene, Y., Vieira Torre Do Vale Froes, A., Jones, C., Beaujean, P., Liegois, V., MacMillan, F., Champagne, B., Clays, K., & Fielden, J. (2023). Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability. Angewandte Chemie International Edition, 62(5), [e202215537]. https://doi.org/10.1002/anie.202215537

Hood, Bethany Rose ; de Coene, Yovan ; Vieira Torre Do Vale Froes, Afonso ; Jones, Claire ; Beaujean, Pierre ; Liegois, Vincent ; MacMillan, Fraser ; Champagne, Benoit ; Clays, Koen ; Fielden, John. / Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability. In: Angewandte Chemie International Edition. 2023 ; Vol. 62, No. 5.

@article{8888309dd22e405eb6001a57238ef62f,

title = "Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability",

abstract = "Electrochemically switched 2nd 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.",

author = "Hood, {Bethany Rose} and {de Coene}, Yovan and {Vieira Torre Do Vale Froes}, Afonso and Claire Jones and Pierre Beaujean and Vincent Liegois and Fraser MacMillan and Benoit Champagne and Koen Clays and John Fielden",

note = "Research Funding: Engineering and Physical Sciences Research Council. Grant Numbers: EP/M00452X/1, EP/S005854/1; University of East Anglia. Grant Numbers: Studentship, Katritzky Scholarship; Leverhulme Trust. Grant Number: RPG-2020-365; Royal Society. Grant Number: Woolfson Research Merit Award; Fonds Wetenschappelijk Onderzoek. Grant Number: 1234222N; FRS-FNRS. Grant Number: Research Associate; FNRS-FRFC. Grant Number: U.G018.19, U.G011.22, RW/GEQ2016, GEQ U.G011.22; Walloon Region. Grant Number: 1610468, RW/GEQ2016, 2110213",

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day = "26",

doi = "10.1002/anie.202215537",

language = "English",

volume = "62",

journal = "Angewandte Chemie International Edition",

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Hood, BR, de Coene, Y, Vieira Torre Do Vale Froes, A, Jones, C, Beaujean, P, Liegois, V, MacMillan, F, Champagne, B, Clays, K & Fielden, J 2023, 'Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability', Angewandte Chemie International Edition, vol. 62, no. 5, e202215537. https://doi.org/10.1002/anie.202215537

Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability. / Hood, Bethany Rose; de Coene, Yovan; Vieira Torre Do Vale Froes, Afonso; Jones, Claire; Beaujean, Pierre; Liegois, Vincent; MacMillan, Fraser; Champagne, Benoit; Clays, Koen; Fielden, John.

In: Angewandte Chemie International Edition, Vol. 62, No. 5, e202215537, 26.01.2023.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability

AU - Hood, Bethany Rose

AU - de Coene, Yovan

AU - Vieira Torre Do Vale Froes, Afonso

AU - Jones, Claire

AU - Beaujean, Pierre

AU - Liegois, Vincent

AU - MacMillan, Fraser

AU - Champagne, Benoit

AU - Clays, Koen

AU - Fielden, John

N1 - Research Funding: Engineering and Physical Sciences Research Council. Grant Numbers: EP/M00452X/1, EP/S005854/1; University of East Anglia. Grant Numbers: Studentship, Katritzky Scholarship; Leverhulme Trust. Grant Number: RPG-2020-365; Royal Society. Grant Number: Woolfson Research Merit Award; Fonds Wetenschappelijk Onderzoek. Grant Number: 1234222N; FRS-FNRS. Grant Number: Research Associate; FNRS-FRFC. Grant Number: U.G018.19, U.G011.22, RW/GEQ2016, GEQ U.G011.22; Walloon Region. Grant Number: 1610468, RW/GEQ2016, 2110213

PY - 2023/1/26

Y1 - 2023/1/26

N2 - Electrochemically switched 2nd 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.

AB - Electrochemically switched 2nd 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.

U2 - 10.1002/anie.202215537

DO - 10.1002/anie.202215537

M3 - Article

VL - 62

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 5

M1 - e202215537

ER -

Electrochemically-switched 2nd order non-linear optical response in an arylimido-polyoxometalate with high contrast and cyclability

Abstract

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Projects

Enhanced single-crystal X-ray diffraction facilities

Polyoxometalate-Based Sensitizers for p-Type Dye-Sensitized Solar Cells

Cite this