Gao Wenze, Cai Liangliang, Kang Faming, Shang Lina, Zhao Mali, Zhang Chi, Xu Wei
Interdisciplinary Materials Research Center, School of Materials Science and Engineering, Tongji University, Shanghai 201804, People's Republic of China.
Department of Physics, National University of Singapore, Singapore 117551, Singapore.
J Am Chem Soc. 2023 Mar 22;145(11):6203-6209. doi: 10.1021/jacs.2c12292. Epub 2023 Mar 10.
Elimination reactions are one of the most important reactions in organic synthesis, especially in the formation of alkenes and alkynes. Herein, based on scanning tunneling microscopy, we report the bottom-up synthesis of one-dimensional carbyne-like nanostructures, metalated carbyne ribbons with the incorporation of Cu or Ag atoms, through α- and β-elimination reactions of tetrabromomethane and hexabromoethane on surfaces. Density functional theory calculations demonstrate a width-dependent band gap modulation within these ribbon structures, which is affected by interchain interactions. Moreover, mechanistic insights into the on-surface elimination reactions have also been provided in this study.
消除反应是有机合成中最重要的反应之一，尤其是在烯烃和炔烃的形成过程中。在此，基于扫描隧道显微镜，我们报道了通过四溴甲烷和六溴乙烷在表面上的α-消除和β-消除反应，自下而上合成一维类卡宾纳米结构，即掺入铜或银原子的金属化卡宾带。密度泛函理论计算表明，这些带结构内存在宽度依赖的带隙调制，这受到链间相互作用的影响。此外，本研究还提供了对表面消除反应的机理见解。
