Electrooxidation-Induced Reverse Switching in Azobenzene-Based Photoswitches

Hussain Z, Schatz D, Oberhof N, Franz E, Schauermann D, Dreuw A, Wegner HA, Brummel O, Libuda J (2025)

Publication Type: Journal article

Publication year: 2025

Journal

Journal of Physical Chemistry C American Chemical Society

Book Volume: 129

Pages Range: 21560-21570

Journal Issue: 49

DOI: 10.1021/acs.jpcc.5c06149

Abstract

Photoswitches, which reversibly switch between isomeric forms upon light exposure, offer promising applications in optical computing, photoresponsive materials, and molecular energy storage. Efficient and controllable back-isomerization is essential for practical applications and can be achieved electrochemically. In this study, we explore how electrochemical oxidation governs the back-conversion of the azobenzene-based photoswitch 4,4′-(diazene-1,2-diyl)bis(N,N′-diethylaniline) (A-AZO). Combining in situ photoelectrochemical infrared reflection absorption spectroscopy with density functional theory calculations, we show that A-AZO undergoes reversible two-step oxidation, forming singly and doubly oxidized species (A-AZO1+and A-AZO2+), with the positive charge primarily localized on the nitrogen atoms of the amino groups. Photochemically, (E)-A-AZO isomerizes to its (Z)-form. Upon electrochemical triggering, the oxidized (Z)-A-AZOx+species act as catalytic intermediates that accelerate the back-conversion to the (E)-isomer. This autocatalytic reaction proceeds with high selectivity and requires minimal external energy input, making it particularly attractive for energy-efficient switching in molecular systems.

Authors with CRIS profile

Zarah Hussain Lehrstuhl für Katalytische Grenzflächenforschung Evanie Franz Lehrstuhl für Katalytische Grenzflächenforschung Daniel Schauermann Lehrstuhl für Katalytische Grenzflächenforschung Olaf Brummel Lehrstuhl für Katalytische Grenzflächenforschung Jörg Libuda Lehrstuhl für Katalytische Grenzflächenforschung

Involved external institutions

Justus-Liebig-Universität Gießen DE Germany (DE) Ruprecht-Karls-Universität Heidelberg DE Germany (DE)

How to cite

APA:

Hussain, Z., Schatz, D., Oberhof, N., Franz, E., Schauermann, D., Dreuw, A.,... Libuda, J. (2025). Electrooxidation-Induced Reverse Switching in Azobenzene-Based Photoswitches. Journal of Physical Chemistry C, 129(49), 21560-21570. https://doi.org/10.1021/acs.jpcc.5c06149

MLA:

Hussain, Zarah, et al. "Electrooxidation-Induced Reverse Switching in Azobenzene-Based Photoswitches." Journal of Physical Chemistry C 129.49 (2025): 21560-21570.

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