Synthesis and Optoelectronic Applications of d_π–p_π Conjugated Polymers with a Di‐metallaaromatic Acceptor

Abstract The development of conjugated polymers especially n‐type polymer semiconductors is powered by the design and synthesis of electron‐deficient building blocks. Herein, a strong acceptor building block with di‐metallaaromatic structure was designed and synthesized by connecting two electron‐deficient metallaaromatic units through a π‐conjugated bridge. Then, a double‐monomer polymerization methodology was developed for inserting it into conjugated polymer scaffolds to yield metallopolymers. The isolated well‐defined model oligomers indicated polymer structures. Kinetic studies based on nuclear magnetic resonance and ultraviolet–visible spectroscopies shed light on the polymerization process. Interestingly, the resulted metallopolymers with d π –p π conjugations are very promising electron transport layer materials which can boost photovoltaic performance of an organic solar cell, with power conversion efficiency up to 18.28 % based on the PM6 : EH‐HD‐4F non‐fullerene system. This work not only provides a facile route to construct metallaaromatic conjugated polymers with various functional groups, but also discovers their potential applications for the first time.