Naphthobischalcogenadiazole Conjugated Polymers: Emerging Materials for Organic Electronics

π‐Conjugated polymers are an important class of materials for organic electronics. In the past decade, numerous polymers with donor–acceptor molecular structures have been developed and used as the active materials for organic devices, such as organic field‐effect transistors (OFETs) and organic photovoltaics (OPVs). The choice of the building unit is the primary step for designing the polymers. Benzochalcogenadiazoles (BXzs) are one of the most familiar acceptor building units studied in this area. As their doubly fused system, naphthobischalcogenadiazoles (NXzs), i.e., naphthobisthiadiazole (NTz), naphthobisoxadiazole (NOz), and naphthobisselenadiazole (NSz) are emerging building units that provide interesting electronic properties and highly self‐assembling nature for π‐conjugated polymers. With these fruitful features, π‐conjugated polymers based on these building units demonstrate great performances in OFETs and OPVs. In particular, in OPVs, NTz‐based polymers have exhibited more than 10% efficiency, which is among the highest values reported so far. In this Progress Report, the synthesis, properties, and structures of NXzs and their polymers is summarized. The device performance is also highlighted and the structure–property relationships of the polymers are discussed.