Center for Nanotechnology , Heisenbergstraße 11 , 48149 Münster , Germany.
Physikalisches Institut , Westfälische Wilhelms-Universität , Wilhelm-Klemm-Straße 10 , 48149 Münster , Germany.
J Am Chem Soc. 2018 May 9;140(18):6000-6005. doi: 10.1021/jacs.8b02599. Epub 2018 Apr 18.
Polymerization of a biphenyl bis α-diazo ketone on Cu(111) and Au(111) surfaces to provide furandiyl bridged poly-para-phenylenes is reported. Polymerization on Cu(111) occurs via initial N fragmentation leading to Cu-biscarbene complexes at room temperature as polymeric organometallic structure. At 135 °C, carbene coupling affords polymeric α,β-unsaturated 1,4-diketones, while analogous alkene formation on the Au(111) surface occurs at room temperature. Further temperature increase leads to deoxygenative cyclization of the 1,4-diketone moieties to provide alternating furandiyl biphenyl copolymers on Cu(111) (165 °C) and Au(111) (240 °C) surfaces. This work shows a new approach to generate Cu-biscarbene intermediates on surfaces, opening the pathway for the controlled generation of biphenyl copolymers.
报道了在 Cu(111) 和 Au(111) 表面上双苯甲酰基-α-重氮酮的聚合，以提供呋喃二基桥联聚-para-苯撑。在室温下，聚合在 Cu(111) 上通过初始 N 断裂发生，导致形成聚合的有机金属结构的 Cu-双卡宾络合物。在 135°C 下，卡宾偶联得到聚合的α,β-不饱和 1,4-二酮，而类似的烯烃在 Au(111) 表面上在室温下形成。进一步提高温度导致 1,4-二酮部分的脱氧环化，在 Cu(111)（165°C）和 Au(111)（240°C）表面上提供交替的呋喃二基联苯共聚物。这项工作展示了在表面上生成 Cu-双卡宾中间体的新方法，为控制生成联苯共聚物开辟了途径。
