Phenazine-Substituted Poly(benzimidazobenzophenanthrolinedione): Electronic Structure, Thin Film Morphology, Electron Transport, and Mechanical Properties of an n‑Type Semiconducting Ladder Polymer

Unlike naphthalene diimides, perylene diimides, and other classes of n-type conjugated polymers with numerous derivatives that enable understanding of structure–property relationships, the electronic structure and properties have not been reported for any derivative of ladder poly­(benzimidazobenzophenanthroline) (BBL). Herein, we report the synthesis and properties of BBL-P, a phenazine derivative of BBL. In acid solution, BBL-P has a broad absorption spectrum with a lowest energy absorption peak at 840 nm due to protonation-enhanced intramolecular charge transfer. Compared to BBL, BBL-P thin films have decreased crystallinity with face-on molecular orientations on substrates, resulting in a substantially decreased field-effect electron mobility of 1.2 × 10–4 cm2/V s. BBL-P films have excellent mechanical properties exemplified by a Young modulus of 11 GPa. The results demonstrate that BBL-P is a promising n-type semiconducting polymer and provide new insights into the effects of backbone structure on electronic structure, thin film microstructure, and charge transport properties of conjugated ladder polymers.