文献类型：期刊文献

英文题名：Two-Dimensional Crystal Transition from Radialene to Cumulene on Ag(111) via Retro-[2+1] Cycloaddition

作者：Liu, Jian-Wei[1];Wang, Ying[1];Kang, Li-Xia[1];Zhao, Yan[1];Xing, Guang-Yan[1];Huang, Zheng-Yang[1];Zhu, Ya-Cheng[1];Li, Deng-Yuan[1];Liu, Pei-Nian[1]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat & Feringa Nobel Prize Scientist Jo, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：145

期号：24

起止页码：13048

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20232714344573);WOS:【SCI-EXPANDED(收录号:WOS:001026256100001)】；

基金：This work was supported by the National Natural Science Foundation of China (nos. 22272050, 21925201, 22161160319, 22002044, and 21978049), Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), the Shanghai Municipal Science and Technology Qi Ming Xing Project (no 22QA1403000), Natural Science Foundation of Shanghai (20ZR1414200), the Programme of Introducing Talents of Discipline to Universities (B16017), China Scholarship Council (CSC no 202106745003), Shanghai Sailing Program (23YF1408700), 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：Annealing - Carbon - Cycloaddition - Density functional theory - Hydrogen - Hydrogen bonds - Reaction intermediates - Scanning tunneling microscopy - Stereoselectivity

摘要：Two-dimensional (2D) crystal-to-crystal transition isan importantmethod in crystal engineering because of its ability to directly creatediverse crystal materials from one crystal. However, steering a 2Dsingle-layer crystal-to-crystal transition on surfaces with high chemo-and stereoselectivity under ultra-high vacuum conditions is a greatchallenge because the transition is a complex dynamic process. Here,we report a highly chemoselective 2D crystal transition from radialeneto cumulene with retention of stereoselectivity on Ag(111) via retro-[2+ 1] cycloaddition of three-membered carbon rings and directly visualizethe transition process involving a stepwise epitaxial growth mechanismby the combination of scanning tunneling microscopy and non-contactatomic force microscopy. Using progression annealing, we found thatisocyanides on Ag(111) at a low annealing temperature underwent sequential[1 + 1 + 1] cycloaddition and enantioselective molecular recognitionbased on C-H & BULL;& BULL;& BULL;Cl hydrogen bonding interactionsto form 2D triaza[3]radialene crystals. In contrast, a higher annealingtemperature induced the transformation of triaza[3]radialenes to generate trans-diaza[3]cumulenes, which were further assembled into2D cumulene-based crystals through twofold N-Ag-N coordinationand C-H & BULL;& BULL;& BULL;Cl hydrogen bonding interactions.By combining the observed distinct transient intermediates and densityfunctional theory calculations, we demonstrate that the retro-[2 +1] cycloaddition reaction proceeds via the ring opening of a three-memberedcarbon ring, sequential dechlorination/hydrogen passivation, and deisocyanation.Our findings provide new insights into the growth mechanism and dynamicsof 2D crystals and have implications for controllable crystal engineering.