Aryne Polymerization Enabling Straightforward Synthesis of Elusive Poly(ortho-arylene)s

Herein we present the first straightforward aryne polymerization that successively connects aromatic rings at their ortho-positions, directly giving poly(ortho-phenylene)s of up to ca. 100-mer size. The polymerization proceeds smoothly in a chain-growth fashion in the presence of a monovalent copper reagent. Direct synthesis of poly(ortho-arylene)s has been a missing piece of aromatic chemistry for a long time (although the discovery of arynes dates back to 1902), in contrast to the well-investigated para- and meta-linked polyarylenes. Our achievement reported here is expected to open up new areas of nanocarbon and materials science.

在此我们展示了首例直接的芳炔聚合反应，它能连续地在芳环的邻位进行连接，直接得到大约100个单元大小的聚（邻亚苯基）。在一价铜试剂存在的情况下，聚合反应以链增长的方式顺利进行。长期以来，聚（邻亚芳基）的直接合成一直是芳香化学中缺失的一部分（尽管芳炔的发现可追溯到1902年），这与研究得较为深入的对位和间位连接的聚亚芳基形成对比。我们在此报道的成果有望开拓纳米碳和材料科学的新领域。