Synthesis of Electron-Deficient BisAzaCoroneneDiimide Conjugated Polymers by Light-Freezing Dynamic Covalent Bonds

We present a novel light-frozen dynamic covalent polymerization methodology to synthesize conjugated polymers based on BisAzaCoroneneDiimides (BACDs). This metal-free process converts reversible poly-imines into kinetically locked conjugated polymers using visible light, generating minimal side-products. By incorporating aldehyde-functionalized comonomers, the approach enables the creation of diverse n-type semiconducting polymers with tunable optical band gaps and low LUMO levels. The polymers exhibit exceptional thermal, electrochemical, and photostability, with strong interchain interactions upon electrochemical reduction observed in solution, attributed to the BACD core. Broad absorp-tion from the visible to near-infrared range underscores their potential in charge and energy transport applications for organic electronics. This scalable, sustainable strategy unlocks access to a versatile class of n-type diimide polymers.