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Synthesis of π‑Conjugated Polymers Containing Phosphole Units in the Main Chain by Reaction of an Organometallic Polymer Having a Titanacyclopentadiene Unit

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journal contribution
posted on 20.01.2015, 00:00 by Yoshimasa Matsumura, Masahiro Ueda, Katsura Fukuda, Kazuhisa Fukui, Ichiro Takase, Hiroki Nishiyama, Shinsuke Inagi, Ikuyoshi Tomita
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 (Mn) and molecular weight distribution (Mw/Mn) 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 (Emax) of 595 nm and a quantum yield (Φ) of 0.10.