Tuning Electrocatalytic Energy Release in Norbornadiene Based Molecular Solar Thermal Systems Through Substituent Effects
Journal article, 2025
Molecular solar thermal (MOST) systems, such as the norbornadiene/quadricyclane (NBD/QC) pair, combine solar energy conversion, storage, and release in a simple one-molecule process. The energy-releasing reaction QC to NBD can be controlled electrochemically. In this study, we used in-situ photoelectrochemical infrared spectroscopy (PEC-IRRAS) together with density functional theory (DFT) calculations to investigate how electron donating (EDG) and electron withdrawing (EWG) groups in the push-pull system of the MOST pair affect the electrocatalytic properties of the electrochemically triggered back-conversion. Specifically, we investigated cyano, tosyl, and methyl ester groups as EWGs, and methoxy, dimethylamine, thioether, and diphenylamine groups located in the para-position of a phenyl group as EDGs. We characterized the onset potential, electrochemical stability window, and selectivity. We found that these properties strongly depend on the strength of electron donation of the EDG, as it exclusively locates the highest occupied molecular orbital (HOMO) and raises its energy level. We obtained the highest selectivity for compounds with p-methoxyphenyl functionality.
isomerization
photoswitches
electrochemistry
IR spectroscopy
push–pull system
Author
Evanie Franz
University of Erlangen-Nuremberg (FAU)
Nils Oberhof
Heidelberg University
Daniel Krappmann
University of Erlangen-Nuremberg (FAU)
Nicolò Baggi
Polytechnic University of Catalonia
Spanish National Research Council (CSIC)
Zarah Hussain
University of Erlangen-Nuremberg (FAU)
Kasper Moth-Poulsen
Polytechnic University of Catalonia
Spanish National Research Council (CSIC)
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Catalan Institution for Research and Advanced Studies
Helen Hölzel
Polytechnic University of Catalonia
Justus Liebig University Giessen
Andreas Hirsch
University of Erlangen-Nuremberg (FAU)
Andreas Dreuw
Heidelberg University
Olaf Brummel
University of Erlangen-Nuremberg (FAU)
Jörg Libuda
University of Erlangen-Nuremberg (FAU)
Chemistry - A European Journal
0947-6539 (ISSN) 1521-3765 (eISSN)
Vol. 31 49 e02294Photo Thermal Management Materials (PHOTERM)
European Commission (EC) (EC/H2020/101002131), 2021-10-01 -- 2026-09-30.
Subject Categories (SSIF 2025)
Theoretical Chemistry
Atom and Molecular Physics and Optics
Inorganic Chemistry
DOI
10.1002/chem.202502294
PubMed
40767484
Related datasets
Tuning Electrocatalytic Energy Release in Norbornadiene Based Molecular Solar Thermal Systems Through Substituent Effects [dataset]
DOI: 10.5281/zenodo.14803619