文献类型：期刊文献

英文题名：Conjugated Shape Persistent Heterocycle Macrocycles for Sacrificial Photocatalytic Hydrogen Evolution

作者：Liu, Xinman[1,2,3,4];Qu, Hang[3,4];Li, Chao[5];Liu, Tao[3,4,6];Xiao, Ziheng[3,4];Feng, Shufan[1,2];Zhu, Qiang[3,4,6];Lu, Yu-Lin[3,4];Zhang, Jiayi[1];Yu, Zhiwu[1,2];Chen, Teng-Teng[5];Zhang, Weiwei[1,2];Boott, Charlotte E.[3,4];Hua, Jianli[1,2];Tian, He[1,2];Cooper, Andrew I.[3,4,6]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, Joint Int Res Lab Precis Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]Univ Liverpool, Mat Innovat Factory, Liverpool L69 7ZD, Lancs, England;[4]Univ Liverpool, Dept Chem, Liverpool L69 7ZD, Lancs, England;[5]Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Clear Water Bay, Hong Kong 999077, Peoples R China;[6]Univ Liverpool, Leverhulme Res Ctr Funct Mat Design, Liverpool L69 7ZD, Merseyside, England

年份：2026

外文期刊名：CCS CHEMISTRY

收录：WOS:【ESCI(收录号:WOS:001822715900001)】；

基金：This work was supported financially by the following institutions: the National Natural Science Foundation of China (grant nos. 22271093 and 21971064) , Science and Technology Commission of Shanghai Municipality, China (grant nos. 24DX1400200 and 24160711900) , Programme of Introducing Talents of Discipline to Universities, China (grant no. B16017) , the Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (grant no. JYB2025XDXM404) and the Fundamental Research Funds for the Central Universities, China. X.L. acknowledges the China Scholarship Council for financial support. A.I.C. thanks the Royal Society for a Research Professorship, UK (RSRP\S2\232003) . The authors also received funding from the Engineering and Physical Sciences Research Council (EP/V026887/1) and from the Leverhulme Trust via the Leverhulme Research Centre for Functional Materials Design, United Kingdom.

语种：英文

外文关键词：macrocycles; heterocycle; photocatalysis; hydrogen production; structure-activity relationships

摘要：Most organic materials investigated for photocatalytic hydrogen production are extended solids, such as carbon nitride, covalent organic frameworks, or conjugated organic polymers. Conjugated molecules with well-defined architectures provide an alternative platform that enables mechanistic investigations at the molecular level. Here, we present the synthesis of chemically stable conjugated macrocycles via aromatic imine condensation, followed by oxidative cyclization. These macrocycles exhibited efficient light absorption, good water affinity, and effective photo-induced charge separation. Combined transient absorption spectroscopy and density functional theory (DFT) analyses revealed that the heterocycle-based triangular macrocycle (TMC) adopted a distinctive C2-symmetric conformation that directed charge carriers toward spatially separated edges of the framework, leading to pronounced charge delocalization and prolonged excited-state lifetimes. In aqueous dispersions, the imidazole-based macrocycle (TMC-N) further formed photoinduced polarons, facilitating charge separation and transport. As a result, protonated TMC-N achieved a sacrificial hydrogen evolution rate (HER) of 1390 mu mol & centerdot; g-1 & centerdot; h-1 under AM 1.5G irradiation (100 mW & centerdot; cm-2). This well-defined platform enabled a multiscale photophysical investigation bridging theoretical models, discrete molecular species, and their supramolecular aggregates under photocatalytic conditions, revealing a structure-symmetry-excited-state dynamics relationship in supramolecular macrocycles and offering a molecular design strategy for organic photocatalysts.