ArticleNature communications2026
Orchestrating photoswitch thermal backconversion using hydrogen bonds to reshape energy landscapes.
Article in Nature communications, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
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.
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