Photochemical polymerizations of dithienothiophenes were investigated. Photo-irradiation to the solution containing dithienothiophene and appropriate electron acceptor gave poly-dithienothiophene having ca. 104 (vs. PSt.) of molecular weight. The cation radical of the monomer was efficiently generated through photoinduced electron transfer from the excited state of the monomer to the electron acceptor. Then the successive coupling reaction resulted in a formation of the polymers.
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