Orchestrating photoswitch thermal backconversion using hydrogen bonds to reshape energy landscapes
Artikel i vetenskaplig tidskrift, 2026
Thermodynamic control of molecular photoswitches remains a fundamental challenge, centered on the stabilization of high-energy metastable states. Inspired by concepts of selective kinetic regulation found in Maxwell’s demon-like systems, we explore hydrogen bonding as a molecular-level selector for modulating the thermal back-conversion of quadricyclane (QC) to norbornadiene (NBD). By strategically incorporating hydrogen-bond donors and acceptors, we show that these interactions build a water “bridge” that restricts rotational degrees of freedom. This bridge significantly elevates the kinetic barrier and redirects the isomerization along an alternative reaction coordinate. In this manner, the hydrogen-bonding system selectively regulates the thermal back-conversion dynamics and enables directional control over the isomerization kinetics, achieving up to a 5000-fold extension of the thermal half-life. This work illustrates how hydrogen bonds can facilitate precise control over back-conversion dynamics and molecular thermal stability in molecular photoswitches.
Författare
Liang Fei
Universitat Politecnica de Catalunya
Zacharias Liasi
Köpenhamns universitet
Jacob Lynge Elholm
Universitat Politecnica de Catalunya
Helen Hölzel
Universitat Politecnica de Catalunya
Justus-Liebig-Universität Gießen
D. Flemming Hansen
University College London (UCL)
Kurt V. Mikkelsen
Köpenhamns universitet
Kasper Moth-Poulsen
Institucio Catalana de Recerca i Estudis Avancats
Consejo Superior de Investigaciones Científicas (CSIC)
Universitat Politecnica de Catalunya
Chalmers, Kemi och kemiteknik, Kemi och biokemi
Nature Communications
2041-1723 (ISSN) 20411723 (eISSN)
Vol. 17 1 10063Photo 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
Organisk kemi
DOI
10.1038/s41467-026-76898-2
PubMed
42768029