Highly Stable Two‐Dimensional Conjugated Polymers Enabled by Scalable and Irreversible C─C Cross‐Coupling Reactions

Two-dimensional conjugated polymers (2DCPs) have garnered significant interest due to their high surface area, tunable topologies, and broad applicability across diverse fields. However, scalable synthetic methods for producing highly stable 2DCPs remain unknown. This study presents a fast and scalable method to synthesize highly stable 2DCPs via irreversible C─C cross-coupling reactions. Mechanistic investigations reveal that precise cross-coupling and π-π aggregate templates drive the rapid formation of regular 2D networks. Notably, the resulting 2DCPs exhibit exceptional chemical stability, serving as robust photocatalysts for C‒N cross-coupling and oxidative hydroxylation reactions. Furthermore, a self-standing 2DCP film demonstrates outstanding performance in optoelectronic synapses, with high resilience to harsh conditions. This work establishes a novel approach for synthesizing stable 2DCPs, enabling various applications under extreme conditions.