文献类型：期刊文献

英文题名：Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures

作者：Li, Deng-Yuan[1];Huang, Zheng-Yang[2];Kang, Li-Xia[2];Wang, Bing-Xin[2];Fu, Jian-Hui[2];Wang, Ying[2];Xing, Guang-Yan[2];Zhao, Yan[2];Zhang, Xin-Yu[2];Liu, Pei-Nian[1,2]

机构：[1]China Pharmaceut Univ, Sch Pharm, State Key Lab Nat Med, Nanjing 211198, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, 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:001348514000010)】；

基金：This work was supported by the National Natural Science Foundation of China (Nos. 22272050, 21925201, 22161160319 and 22302068), the Shanghai Municipal Science and Technology Qi Ming Xing Project (No. 22QA1403000), the Shanghai Sailing Program (23YF1408700), China Postdoctoral Science Foundation (2023M731080), and the Fundamental Research Funds for the Central Universities.

语种：英文

摘要：Cyclodehydrogenation is an important ring-formation reaction that can directly produce planar-conjugated carbon-based nanomaterials from nonplanar molecules. However, inherently high C-H bond energy necessitates a high temperature during dehydrogenation, and the ubiquity of C - H bonds in molecules and small differences in their bond energies hinder the selectivity of dehydrogenation. Here, we report a room-temperature cyclodehydrogenation reaction on Au(111) via radical addition of open-shell resonance structures and demonstrate that radical addition significantly decreases cyclodehydrogenation temperature and further improves the chemoselectivity of dehydrogenation. Using scanning tunneling microscopy and non-contact atomic force microscopy, we visualize the cascade reaction process involved in cyclodehydrogenation and determine atomic structures and molecular orbitals of the planar acetylene-linked oxa-nanographene products. The nonplanar intermediates observed during progression annealing, combined with density functional theory calculations, suggest that room-temperature cyclodehydrogenation involves the formation of transient radicals, intramolecular radical addition, and hydrogen elimination; and that the high chemoselectivity of cyclodehydrogenation arises from the reversibility and different thermodynamics of radical addition step. Cyclodehydrogenation is an important ring-formation reaction but the inherently high C-H bond energy necessitates high temperatures, and the ubiquity of C - H bonds in molecules hinders the selectivity. Here, the authors report a selective room-temperature cyclodehydrogenation reaction on Au(111) via radical addition of open-shell resonance structures.