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 (<i>T</i>_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.