Center for Nanotechnology, Heisenbergstraße 11, 48149 Münster, Germany.
J Am Chem Soc. 2014 Jul 9;136(27):9658-63. doi: 10.1021/ja5033875. Epub 2014 Jun 26.
Metal-catalyzed polymerization of 2,6-naphthalenedicarboxylic acid (NDCA) to form poly-2,6-naphthalenes at various surfaces is reported. Polymerizations occur via initial formal dehydrogenation of self-assembled diacids with subsequent decarboxylation to give polymeric bisnaphthyl-Cu species at elevated temperature as intermediate structures (<160 °C). Further temperature increase eventually leads to poly-naphthalenes via reductive elimination. It is demonstrated that the Cu(111) surface works most efficiently to conduct such polymerizations as compared to the Au(111), Ag(111), Cu(100), and Cu(110) surfaces. Poly-2,6-naphthalene with a chain length of over 50 nm is obtained by using this approach. The decarboxylative coupling of aromatic diacids is a very promising tool which further enlarges the portfolio of reactions allowing for on-surface polymerizations and novel organometallic systems preparations.
报道了在各种表面上通过金属催化 2,6-萘二甲酸（NDCA）聚合形成聚 2,6-萘的反应。聚合反应通过自组装二酸的初始形式脱氢和随后的脱羧进行，在高温下形成聚合物双萘基-Cu 物种作为中间结构（<160°C）。进一步升高温度最终通过还原消除生成聚萘。与 Au(111)、Ag(111)、Cu(100) 和 Cu(110) 表面相比，Cu(111)表面在进行此类聚合反应方面最为有效。通过这种方法可以获得链长超过 50nm 的聚 2,6-萘。芳香二酸的脱羧偶联是一种非常有前途的工具，它进一步扩大了允许在表面上进行聚合和制备新型有机金属体系的反应组合。
