Chemoselective On-surface Homocoupling of Terminal Alkynes Catalyzed by Exogenous Cupric Ions.
Chemoselective On-surface Homocoupling of Terminal Alkynes Catalyzed by Exogenous Cupric Ions.
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DOI：
10.1002/asia.202000593
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发表时间：
2020-08
期刊：
影响因子：
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通讯作者：
Jie-Yu Yue;W. Fan;Ting Chen;Zhaohui Wang;Dong Wang;L. Wan
中科院分区：
文献类型：
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作者：
Jie-Yu Yue;W. Fan;Ting Chen;Zhaohui Wang;Dong Wang;L. Wan
采用扫描隧道显微镜研究了外源铜离子催化末端炔在高取向热解石墨（HOPG）表面的偶联反应。在外源铜离子存在的情况下，末端炔的均偶联产生的纳米结构是唯一的产物，而在没有铜离子的情况下，末端炔在表面不发生偶联反应，这表明外源铜离子可以有效催化末端炔的高化学选择性表面反应。HOPG表面对表面产物的生长和排列表现出模板效应。结果表明，以双位单体3,6-二乙基咔唑和三位单体1,3,5-三-（4-乙基苯基）苯为原料，分别制备了二维双炔连接之字形聚合物阵列和二维双炔连接多孔聚合物。该合成策略结合了铜离子催化剂的高选择性和表面合成方法的模板效应，可作为在固体表面上制备双炔连接纳米结构和纳米材料的通用策略。
The on-surface coupling reactions of terminal alkynes catalyzed by exogenous cupric ions on chemically inert highly oriented pyrolytic graphite (HOPG) surface have been investigated by scanning tunnelling microscopy. In the presence of exogenous cupric ions, diyne-linked nanostructures generated via homocoupling of terminal alkynes are the exclusive products, whereas no coupling reaction occurs for the terminal alkynes on the surface in the absence of the cupric ions, suggesting that exogenous cupric ions are efficient to catalyze the highly chemoselective on-surface reaction of terminal alkynes. The HOPG surface displays a template effect to the growth and alignment of the products on the surface. As a result, 2D arrays of diyne-linked zigzag polymers and 2D diyne-linked porous polymers are fabricated from ditopic monomer 3,6-diethynylcarbazole and tritopic monomer 1,3,5-tris-(4-ethynylphenyl) benzene, respectively. This synthetic strategy combining the high selectivity of cupric ion catalyst as well as the template effect of on-surface synthesis approach could be a general strategy to fabricate diyne-linked nanostructures and nanomaterials on solid surfaces.