Tuning Electrocatalytic Energy Release in Norbornadiene Based Molecular Solar Thermal Systems Through Substituent Effects
Artikel i vetenskaplig tidskrift, 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
Författare
Evanie Franz
Friedrich-Alexander-Universität Erlangen Nurnberg (FAU)
Nils Oberhof
Universität Heidelberg
Daniel Krappmann
Friedrich-Alexander-Universität Erlangen Nurnberg (FAU)
Nicolò Baggi
Universitat Politecnica de Catalunya
Consejo Superior de Investigaciones Científicas (CSIC)
Zarah Hussain
Friedrich-Alexander-Universität Erlangen Nurnberg (FAU)
Kasper Moth-Poulsen
Universitat Politecnica de Catalunya
Consejo Superior de Investigaciones Científicas (CSIC)
Chalmers, Kemi och kemiteknik, Tillämpad kemi
Institucio Catalana de Recerca i Estudis Avancats
Helen Hölzel
Universitat Politecnica de Catalunya
Justus-Liebig-Universität Gießen
Andreas Hirsch
Friedrich-Alexander-Universität Erlangen Nurnberg (FAU)
Andreas Dreuw
Universität Heidelberg
Olaf Brummel
Friedrich-Alexander-Universität Erlangen Nurnberg (FAU)
Jörg Libuda
Friedrich-Alexander-Universität Erlangen Nurnberg (FAU)
Chemistry - A European Journal
0947-6539 (ISSN) 1521-3765 (eISSN)
Vol. 31 49 e02294Photo Thermal Management Materials (PHOTERM)
Europeiska kommissionen (EU) (EC/H2020/101002131), 2021-10-01 -- 2026-09-30.
Ämneskategorier (SSIF 2025)
Teoretisk kemi
Atom- och molekylfysik och optik
Oorganisk kemi
DOI
10.1002/chem.202502294
PubMed
40767484
Relaterade dataset
Tuning Electrocatalytic Energy Release in Norbornadiene Based Molecular Solar Thermal Systems Through Substituent Effects [dataset]
DOI: 10.5281/zenodo.14803619