文献类型：期刊文献

英文题名：A Light-Driven ConstitutionalPump

作者：Li, Chong[1];Wu, Huiping[1];Mao, Yijie[1];Yao, Yu[1];Gu, Ruirui[1];Li, Pengyun[1];Wang, Rui[1];Zhang, Qi[1];Zhu, Wei-Hong[1];Tian, He[1];Lehn, Jean-Marie[3];Feringa, Ben L.[1,2];Qu, Da-Hui[1]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[2]Univ Groningen, Stratingh Inst Chem, Zernike Inst Adv Mat, Nijenborgh 4, NL-9747 AG Groningen, Netherlands;[3]Univ Strasbourg, Inst Sci & Ingn Supramol ISIS, Lab Chim Supramol, F-67000 Strasbourg, France

年份：2026

卷号：148

期号：31

起止页码：33925

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20263321311275);Scopus(收录号：2-s2.0-105046998387);WOS:【SCI-EXPANDED(收录号:WOS:001828082600001)】；

基金：This work was supported by the National Natural Science Foundation of China (22588101, 22220102004, 22571084), Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM404), the European Research Council (ERC; advanced grant No. 694345 to B.L.F.), the Dutch Ministry of Education, Culture and Science (Gravitation program No.024.601.035), Science and Technology Commission of Shanghai Municipality (24DX1400200), the Innovation Program of Shanghai Municipal Education Commission (2023ZKZD40), the Programme of Introducing Talents of Discipline to Universities (grant no. B16017), the Fundamental Research Funds for the Central Universities and the Guangxi Science and Technology Innovation Platform Program ('' Leitai '' Action Plan-Guangxi Laboratory Capacity Building) (LT2504240013), and the CNPC Innovation Found (2024DQ020410).

语种：英文

外文关键词：Biomimetics - Covalent bonds - Energy dissipation - Optical pumping - Pumps - Reaction kinetics

摘要：Achieving high degrees of nonequilibrium in dynamic covalent chemistry remains a major challenge for emulating energy-dissipative, biomimetic constitutional 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 nonequilibrium 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 nonequilibrium steady state (NESS), exhibiting pronounced constitutional selection while remaining fully reversible upon removal of the light input. This work establishes a new strategy for approaching highly nonequilibrium dynamic covalent systems and lays the groundwork for the development of life-like nonequilibrium matter.