文献类型：期刊文献

英文题名：Two-Dimensional Nonbenzenoid Heteroacene Crystals Synthesized via In-Situ Embedding of Ladder Bipyrazinylenes on Au(111)

作者：Wang, Ying[1];Gong, Wen-Wen[1];Zhao, Yan[1];Xing, Guang-Yan[1];Kang, Li-Xia[1];Sha, Feng[1];Huang, Zheng-Yang[1];Liu, Jian-Wei[1];Han, Yan-Jie[1];Li, Peng[1];Li, Deng-Yuan[1,2];Liu, Pei-Nian[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, State Key Lab Chem Engn, Key Lab Adv Mat & Feringa Nobel Prize Scientist Jo, Shanghai 200237, Peoples R China;[2]China Pharmaceut Univ, Dept Med Chem, State Key Lab Nat Med, Nanjing 211198, Peoples R China

年份：2024

卷号：63

期号：11

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20240615521489);WOS:【SCI-EXPANDED(收录号:WOS:001156991300001)】；

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. We thank the Research Center of Analysis and Testing of East China University of Science and Technology for help in the characterization.

语种：英文

外文关键词：On-Surface Synthesis; 2D Molecular Crystal; Topological Defect; Heteroacene; Scanning Tunneling Microscopy

摘要：Precisely introducing topological defects is an important strategy in nanographene crystal engineering because defects can tune pi-electronic structures and control molecular assemblies. The synergistic control of the synthesis and assembly of nanographenes by embedding the topological defects to afford two-dimensional (2D) crystals on surfaces is still a great challenge. By in-situ embedding ladder bipyrazinylene (LBPy) into acene, the narrowest nanographene with zigzag edges, we have achieved the precise preparation of 2D nonbenzenoid heteroacene crystals on Au(111). Through intramolecular electrocyclization of o-diisocyanides and Au adatom-directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and lead to the molecular 2D assembly via LBPy-derived interlocking hydrogen bonds. Using bond-resolved scanning tunneling microscopy, we determined the atomic structures of the nonbenzenoid heteroacene product and diverse organometallic intermediates. The tunneling spectroscopy measurements revealed the electronic structure of the nonbenzenoid heteroacene, which is supported by density functional theory (DFT) calculations. The observed distinct organometallic intermediates during progression annealing combined with DFT calculations demonstrated that LBPy formation proceeds via electrocyclization of o-diisocyanides, trapping of heteroarynes by Au adatoms, and stepwise elimination of Au adatoms. Two-dimensional (2D) nonbenzenoid heteroacene crystals are synthesized via the in-situ embedding of ladder bipyrazinylenes (LBPys) on Au(111). Through the intramolecular electrocyclization of o-diisocyanides and Au adatom-directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and give rise to the molecular 2D assembly via LBPy-derived interlocking hydrogen bonds.+ image