Ni(0)/NHC-Mediated Coordination Disproportionation Polymerization of Aromatic Dialdehydes to High-Performance Polyesters

The synthesis of high-performance aromatic polyesters under mild conditions remains challenging using conventional polycondensation strategies. Here, we report a Ni(0)/N-heterocyclic carbene (NHC)-catalyzed coordination disproportionation polymerization (CDP) that enables the direct and byproduct-free transformation of readily accessible aromatic dialdehydes into high-molar-mass polyesters. Tuning the steric and electronic properties of NHC ligands regulates Ni(0)/NHC coordination equilibrium, thereby controlling polyester formation while suppressing benzoin condensation. The CDP process involves stochastic oxidation–reduction coupling of aldehyde groups, yielding sequence-disordered polyesters with high thermal stability ( T d,5% up to 370 °C) and glass transition temperatures above 100 °C, surpassing poly(ethylene terephthalate) in heat resistance. These polyesters exhibit exceptional hydrolytic stability across pH 0–14 at ambient temperature, yet remain fully degradable upon heating in an alkaline organic solvent, achieving an optimal balance between durability and end-of-life recyclability. This work establishes CDP as a versatile platform for constructing high-performance aromatic polyesters from diverse dialdehyde monomers.