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

Uchiyama et al. have reported the first straightforward aryne polymerization that connects aromatic rings at their ortho-positions to give poly(ortho -arylene)s of up to ca. 100-mer size. They use 4,5-dimethoxy-2-(trimethylsilyl)phenyl trifluoromethanesulfonate as an aryne precursor and CuCN as a crucial initiator in the polymerization. In this report, they demonstrate that the polymerization proceeds in chain-growth fashion, not through step growth because the molecular weight of the poly(ortho -arylene)s are modulated by the initiator amount. In addition, they presume the reaction pathway of this polymerization by means of density functional theory (DFT) calculations.