A Light-Driven Constitutional Pump

Le résumé fourni par la source

Achieving high degrees of non-equilibrium in dynamic covalent chemistry remains a major challenge for the synthesis of energy-dissipative matter with life-like behaviors based on reversible covalent bond reorganization. At the molecular level, the central difficulty lies in maximizing the kinetic asymmetry introduced by energy‑driven auxiliary pathways over thermally equilibrating dynamic covalent reactions, whose microscopic reversibility and rapid equilibration intrinsically limit its amplification. Here we report a light-driven constitutional pump that addresses this limitation by embedding a unidirectional, kinetically dominant pathway onto a reversible dynamic covalent metathesis reaction, enabling the system to reach high degrees of non-equilibrium under continuous irradiation. This pumping mechanism is encoded at the molecular design level through conjugative coupling between a diarylethene photoswitch and a polar olefin moiety, which simultaneously enables photonic gating to suppress reverse pathways and generates a high-energy photoisomer intermediate that imposes a strong kinetic preference. As a result, the reaction network is efficiently driven toward a non-equilibrium steady state (NESS), exhibiting pronounced constitutional selection while remaining fully reversible upon removal of the light input. Integration of this pump into polymer networks enables spatiotemporal control over crosslink density, giving rise to photo-adaptive synthetic materials that display non-equilibrium mechanical modulation.

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