文献类型：期刊文献

英文题名：Universal inter-molecular radical transfer reactions on metal surfaces

作者：Wang, Junbo[1,2];Niu, Kaifeng[2,3];Zhu, Huaming[1];Xu, Chaojie[2];Deng, Chuan[1];Zhao, Wenchao[4];Huang, Peipei[1];Lin, Haiping[1];Li, Dengyuan[5];Rosen, Johanna[3];Liu, Peinian[5];Allegretti, Francesco[4];Barth, Johannes V.[4];Yang, Biao[2,4];Bjork, Jonas[3];Li, Qing[1];Chi, Lifeng[2,6]

机构：[1]Shaanxi Normal Univ, Sch Phys & Informat Technol, Xian 710119, Peoples R China;[2]Soochow Univ, Inst Funct Nano & Soft Mat FUNSOM, Jiangsu Key Lab Carbon Based Funct Mat & Devices, Suzhou 215123, Peoples R China;[3]Linkoping Univ, Dept Phys, Chem & Biol, IFM, S-58183 Linkoping, Sweden;[4]Tech Univ Munich, Phys Dept E20, James-Franck-Str 1, D-85748 Garching, Germany;[5]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[6]Macau Univ Sci & Technol, Dept Mat Sci & Engn, Macau 999078, Peoples R China

年份：2024

卷号：15

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001198902100047)】；

基金：We acknowledge the financial support by the Fundamental Research Funds for the Central Universities (Grant GK202201001 (Q.L.), GK202203002 (H.L.)), the National Natural Science Foundation of China (22272099 (Q.L.), 22072102 (Q.L.), 51821002 (L.C.), 22202125 (P.H.)), and the Collaborative Innovation Center of Suzhou Nano Science & Technology, the Suzhou Key Laboratory of Surface and Interface Intelligent Matter (Grant SZS2022011 (L.C.)), and the 111 Project. Funding is further acknowledged from the Swedish Research Council and the Goran Gustafsson Foundation for Research in Natural Sciences and Medicine. The computations were enabled by resources provided by the National Academic Infrastructure for Supercomputing in Sweden (NAISS) and the Swedish National Infrastructure for Computing (SNIC), funded by the Swedish Research Council through grant agreements no. 2022-06725 (J.B.) and no. 2018-05973 (J.B.). We thank Svetlana Klyatskaya and Mario Ruben for providing Ext-TEB molecules in TPD/TP-XPS experiments, Pablo Vezzoni and Peter Feulner for support and advise with the TPD/TP-XPS experimental setup and data analysis.

语种：英文

摘要：On-surface synthesis provides tools to prepare low-dimensional supramolecular structures. Traditionally, reactive radicals are a class of single-electron species, serving as exceptional electron-withdrawing groups. On metal surfaces, however, such species are affected by conduction band screening effects that may even quench their unpaired electron characteristics. As a result, radicals are expected to be less active, and reactions catalyzed by surface-stabilized radicals are rarely reported. Herein, we describe a class of inter-molecular radical transfer reactions on metal surfaces. With the assistance of aryl halide precursors, the coupling of terminal alkynes is steered from non-dehydrogenated to dehydrogenated products, resulting in alkynyl-Ag-alkynyl bonds. Dehalogenated molecules are fully passivated by detached hydrogen atoms. The reaction mechanism is unraveled by various surface-sensitive technologies and density functional theory calculations. Moreover, we reveal the universality of this mechanism on metal surfaces. Our studies enrich the on-surface synthesis toolbox and develop a pathway for producing low-dimensional organic materials. Radicals are expected to be inactive on metal surfaces. Here the authors describe general intermolecular radical transfer reactions on Ag and Cu surfaces and confirm the reaction mechanism by extensive control experiments.