文献类型：期刊文献

英文题名：Isomerization of Organometallic Polymers on Ag(111): Revealing the Intermolecular Hydrogen Transfer Mechanism

作者：Zhang, Xin-Yu[1];Fu, Jian-Hui[1];Chen, Zhen-Qiang[1];Gong, Wen-Wen[1];Wang, Ying[1];Kang, Li-Xia[1];Zhao, Yan[1];Shu, Chen-Hui[3,4];Li, Deng-Yuan[2];Liu, Pei-Nian[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai Key Lab Funct Mat Chem, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]China Pharmaceut Univ, Sch Pharm, State Key Lab Nat Med, Nanjing 211198, Peoples R China;[3]Henan Univ, Sch Future Technol, Kaifeng 475004, Peoples R China;[4]Henan Acad Sci, Inst Quantum Mat & Phys, Zhengzhou 450046, Peoples R China

年份：2025

卷号：19

期号：17

起止页码：16545

外文期刊名：ACS NANO

收录：;EI(收录号：20251718292154);WOS:【SCI-EXPANDED(收录号:WOS:001473291300001)】；

基金：This work was supported by the National Natural Science Foundation of China (22272050, 22161160319, 22302068, and 22002044), the Shanghai Municipal Science and Technology Qi Ming Xing Project (22QA1403000), the Shanghai Sailing Program (23YF1408700), and the China Postdoctoral Science Foundation (2023M731080).

语种：英文

外文关键词：on-surface synthesis; isomerization; intermolecularhydrogen transfer; dehalogenation; organometallicpolymer; scanning tunneling microscopy

摘要：Dehalogenation plays a crucial role in on-surface synthesis, but the bond-forming sites in dehalogenation occasionally differ from the original halogen-substituted sites, leading to unexpected products. Revealing its mechanism is essential for the atomically precise fabrication of low-dimensional nanomaterials, although it remains elusive. Herein, we report an isomerization of organometallic polymers derived from debromination on Ag(111) and elucidate the mechanism involving intermolecular hydrogen transfer via combining scanning tunneling microscopy, noncontact atomic force microscopy, and density functional theory calculations. At room temperature, the precursor 1,4-bis(3-bromothiophen-2-yl)benzene undergoes surface-assisted debromination on Ag(111), forming two organometallic polymers where the bond-forming sites correspond to the original debromination sites. Upon annealing to 393 K, the isomerization of organometallic polymers generates a linear organometallic polymer, where the bond-forming sites mismatched with the original debromination sites. Control experiments combined with theoretical calculations demonstrate that the unexpected isomerization proceeds through the dissociation of polymer chains into surface-stabilized diradical monomers or oligomers, intermolecular hydrogen transfer, and the final recombination of surface-stabilized radicals with Ag adatoms.