| Abstract: | 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. |
