Shimomoto Hiroaki, Moriya Taka-Aki, Mori Takeshi, Itoh Tomomichi, Kanehashi Shinji, Ogino Kenji, Ihara Eiji
Department of Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan.
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan.
ACS Omega. 2020 Mar 4;5(10):4787-4797. doi: 10.1021/acsomega.9b03408. eCollection 2020 Mar 17.
The original synthetic strategy for a new type of poly(arylene vinylene) (PAV) is presented, where the C=C-bond-forming coupling of bis(alkoxycarbonyldiazomethyl)aromatic compounds is utilized as propagation. The strategy is unique in that the resulting PAVs have an alkoxycarbonyl group as an electron-withdrawing substituent on each vinylene carbon atom in the polymer main chain. Among the transition-metal catalysts examined in this study, RuCl(cod)Cp* (cod = 1,5-cyclooctadiene, Cp* = pentamethylcyclopentadienyl) is the most efficient, affording PAVs from a series of bis(alkoxycarbonyldiazomethyl)aromatic compounds with a high -C=C-forming selectivity of up to 90%. A PAV sample with a fluorenylene framework as an arylene moiety prepared by the Ru catalyst exhibited a hole mobility of 4 × 10 cm V s.
本文提出了一种新型聚亚芳基乙烯（PAV）的合成策略，该策略利用双（烷氧羰基重氮甲基）芳族化合物的C=C键形成偶联反应进行链增长。该策略的独特之处在于，所得的PAV在聚合物主链的每个亚乙烯基碳原子上都有一个作为吸电子取代基的烷氧羰基。在本研究中考察的过渡金属催化剂中，RuCl(cod)Cp*（cod = 1,5-环辛二烯，Cp* = 五甲基环戊二烯基）效率最高，能从一系列双（烷氧羰基重氮甲基）芳族化合物中制得PAV，形成C=C键的选择性高达90%。通过Ru催化剂制备的以芴撑骨架作为亚芳基部分的PAV样品，其空穴迁移率为4×10 cm²V⁻¹s⁻¹ 。
