Donor–acceptor–donor oligomers with dibenzothiophene 5,5-dioxide core and end-cap phenylene–thiophene substitutes were newly synthesized. New oligomers were characterized by UV–vis absorption and photoluminescence spectroscopy, cyclic voltammetry, and applied as electron donor in bulk-heterojunction solar cells. The results indicate that phenylene–thiophene oligomer derivatives containing dibenzothiophene 5,5-dioxide moiety are appraised to be valuable electron donors.

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