Enhancing Built-in Electric Field via Molecular Dipole Control in Conjugated Microporous Polymers for Boosting Charge Separation

The built-in electric field (BEF) has been considered as the key kinetic factor for facilitating efficient photoinduced carrier separation and migration of polymeric photocatalysts. Enhancing the BEF of the polymers could enable a directional migration of the photogenerated carriers to accelerate photogenerated charge separation and thus boost photocatalytic performances. However, achieving this approach remains a formidable challenge, which has never been realized in conjugated microporous polymers (CMPs). Herein, we developed a molecular dipole control strategy to modulate the BEF in CMPs by varying the nature of the core. As a result, a series of CMPs with a tunable BEF were designed and prepared via FeCl₃-mediated coupling of bicarbazole with different acceptor cores. The optimized CbzCMP-9 featured the strongest BEF induced by its high molecular dipole, which grants it with a powerful driving force to accelerate exciton dissociation into electron–hole pairs and facilitates charge transfer along the backbone of CMPs to the surface, resulting in a remarkable photocatalytic performance toward thiocyano chromones and C-3 thiocyanation of indoles (up to 95 and 98% yields, respectively) and prominently surpassing many other reported photocatalysts. In brief, the proposed strategy highlights that enhancing the BEF by modulating molecular dipole can lead to a dramatic improvement in photocatalytic performance, which is expected to be employed for constructing other photocatalytic systems with high performance.