New Chemistry Exploited by Coordination Polymerization of Aromatic Monomers

本研究的目的是将通常用于制备脂肪族聚合物的配位插入聚合的概念扩展到芳香族聚合物的合成。钯催化剂催化[2.2.1]杂环烯烃的配位-插入聚合，得到了聚邻芳烯。钯催化[2.2.1]杂环烯烃与一氧化碳共聚，脱水后得到芳香聚酮和聚缩醛。将得到的聚邻芳烯在氯化铁的存在下氧化，生成石墨烯纳米带。本研究为合成邻芳基聚合物提供了一种通用、高效的方法。

The purpose of the present research is to expand the concept of coordination-insertion polymerization, which is usually used to prepare aliphatic polymers, to the synthesis of aromatic polymers. The coordination-insertion polymerization of [2.2.1]oxabicyclic alkenes, as aryne equivalents, by palladium catalysts followed by dehydration afforded poly(ortho-arylene)s. The palladium-catalyzed copolymerization of [2.2.1]oxabicyclic alkenes with carbon monoxide followed by dehydration afforded aromatic polyketones and polyacetals. The obtained poly(ortho-arylene)s were then oxidized in the presence of ferric chloride to produce graphene nanorribons. The present study provide a versatile and efficient method to synthesize aromatic polymers having ortho-arylene units.