Matsumura Yoshimasa, Ueda Masahiro, Fukuda Katsura, Fukui Kazuhisa, Takase Ichiro, Nishiyama Hiroki, Inagi Shinsuke, Tomita Ikuyoshi
Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta-cho 4259-G1-9, Midori-ku, Yokohama 226-8502, Japan.
Central Research Center, Daicel Corporation, Shinzaike 1239, Aboshi-ku, Himeji, Hyogo, Japan.
ACS Macro Lett. 2015 Jan 20;4(1):124-127. doi: 10.1021/mz500693r. Epub 2015 Jan 7.
A regioregular organometallic polymer possessing titanacyclopentadiene units in the main chain, which was obtained by the reaction of terminal diyne and a low-valent titanium complex, was subjected to the reaction with dichlorophosphines to give π-conjugated polymers with phosphole or phosphole oxide units in the main chain. For example, a phenylphosphole-containing polymer was obtained in 76% yield by the reaction with dichlorophenylphosphine, whose number-average molecular weight () and molecular weight distribution (/) were estimated to be 6100 and 1.9, respectively, by GPC. The polymer was found to have an extended π-conjugated system, and its lowest unoccupied molecular orbital (LUMO) energy level was remarkably low (-3.28 eV) as supported by its UV-vis absorption spectrum and cyclic voltammetric (CV) analysis. Also, the polymer exhibits orange photoluminescence with an emission maximum () of 595 nm and a quantum yield (Φ) of 0.10.
一种主链含有钛杂环戊二烯单元的区域规整有机金属聚合物，它是通过端基二炔与低价钛配合物反应得到的，该聚合物与二氯膦反应，得到主链含有膦环戊二烯或膦环戊二烯氧化物单元的π共轭聚合物。例如，通过与二氯苯基膦反应以76%的产率得到了含苯基膦环戊二烯的聚合物，通过凝胶渗透色谱法（GPC）估计其数均分子量（）和分子量分布（/）分别为6100和1.9。发现该聚合物具有扩展的π共轭体系，其紫外可见吸收光谱和循环伏安（CV）分析表明其最低未占分子轨道（LUMO）能级非常低（-3.28 eV）。此外，该聚合物呈现橙色光致发光，发射最大值（）为595 nm，量子产率（Φ）为0.10。
