Selective Synthesis and Properties of Electron-Deficient Hybrid Naphthalene-Based π-Conjugated Systems.

One driving force for advancing the field of semiconducting polymers is to create new π-conjugated systems as building units. This work reports on a series of electron-deficient hybrid naphthalene-based π-conjugated systems in which two different units among benzoxadiazole, benzothiadiazole, benzoselenadiazole, and benzopyrazine (quinoxaline) were fused. These π-conjugated systems were synthesized in excellent yields via the selective one-side ring-opening reaction of corresponding naphthobischalcogenadiazoles using the NaBH4 /CoCl2 reduction reagents, followed by the ring-closing reactions. The electronic structure of these π-conjugated systems was studied in comparison with their parent systems. Furthermore, thiadiazolonaphthoxadiazole was incorporated into the π-conjugated polymer backbone. The electronic structure, film structure, and photovoltaic properties of the polymer were studied as well.