Mediator-Assisted Energy Release Enabled by Positional Isomerism in Norbornadiene/Quadricyclane Systems
4 affiliations
- 1Interface Research and Catalysis, Erlangen Center for Interface Research and Catalysis, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, Erlangen, Germany, 91058
- 2Interdisciplinary Center for Scientific Computing, Universität Heidelberg, Im Neuenheimer Feld 205 A, Heidelberg, Germany, 69120
- 3Institut Organische Chemie, Justus-Liebig-Universität Giessen, Heinrich-Buff-Ring 17, Gießen, Germany, 35392
- 4Department of Chemical Engineering, Universitat Politècnica de Catalunya, Eduard Maristany 10-14, Barcelona, Spain, 08019
Abstract
Molecular solar thermal (MOST) systems store solar energy in metastable photoisomers and release it on demand through triggered back-conversion. Here, we show that mixtures of MOST compounds enable a distinct energy-release strategy in which one component mediates the activation of another. Using methoxyphenyl-substituted norbornadiene/quadricyclane (NBD/QC) positional isomers, we show by in situ photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) and density functional theory (DFT) that substituent position shifts the electrochemical onset potential by up to 0.6 V and controls switching selectivity, largely independently of thermal stability, a trend rationalized by calculated ionization potentials. Crucially, in a mixture, the electrochemically facile QC isomer triggers back-conversion of a second QC isomer below its intrinsic onset potential, consistent with a radical-chain mechanism. Mediator-assisted triggering thus decouples the requirements for molecular energy storage and electrochemical activation and opens new opportunities for tuning energy release strategies through multicomponent MOST systems.
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BibTeX
@misc{hussain2026mediatorassisted,
title = {{Mediator-Assisted Energy Release Enabled by Positional Isomerism in Norbornadiene/Quadricyclane Systems}},
author = {Zarah Hussain and Adrian J. Müller and Evanie Franz and Andreas Dreuw and Helen Hölzel and Olaf Brummel and Jörg Libuda},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010832/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010832/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Mediator-Assisted Energy Release Enabled by Positional Isomerism in Norbornadiene/Quadricyclane Systems
AU - Zarah Hussain
AU - Adrian J. Müller
AU - Evanie Franz
AU - Andreas Dreuw
AU - Helen Hölzel
AU - Olaf Brummel
AU - Jörg Libuda
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010832/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010832/v1
AB - Molecular solar thermal (MOST) systems store solar energy in metastable photoisomers and release it on demand through triggered back-conversion. Here, we show that mixtures of MOST compounds enable a distinct energy-release strategy in which one component mediates the activation of another. Using methoxyphenyl-substituted norbornadiene/quadricyclane (NBD/QC) positional isomers, we show by in situ photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) and density functional theory (DFT) that substituent position shifts the electrochemical onset potential by up to 0.6 V and controls switching selectivity, largely independently of thermal stability, a trend rationalized by calculated ionization potentials. Crucially, in a mixture, the electrochemically facile QC isomer triggers back-conversion of a second QC isomer below its intrinsic onset potential, consistent with a radical-chain mechanism. Mediator-assisted triggering thus decouples the requirements for molecular energy storage and electrochemical activation and opens new opportunities for tuning energy release strategies through multicomponent MOST systems.
ER -