Orchestrating photoswitch thermal backconversion using hydrogen bonds to reshape energy landscapes
Journal article, 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.
Author
Liang Fei
Polytechnic University of Catalonia
Zacharias Liasi
University of Copenhagen
Jacob Lynge Elholm
Polytechnic University of Catalonia
Helen Hölzel
Polytechnic University of Catalonia
Justus Liebig University Giessen
D. Flemming Hansen
University College London (UCL)
Kurt V. Mikkelsen
University of Copenhagen
Kasper Moth-Poulsen
Catalan Institution for Research and Advanced Studies
Spanish National Research Council (CSIC)
Polytechnic University of Catalonia
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
Nature Communications
2041-1723 (ISSN) 20411723 (eISSN)
Vol. 17 1 10063Photo 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
Organic Chemistry
DOI
10.1038/s41467-026-76898-2
PubMed
42768029