Unanticipated Strong Blue Photoluminescence from Fully Biobased Aliphatic Hyperbranched Polyesters

Nonconventional fluorescent polymers without π-aromatic structure have attracted extensive interest in recent years. Hyperbranched polyesters are generally known because of their industrial applications; however, the luminescent properties of the polyester has not been reported. Herein, we synthesized a series of fully biobased aliphatic hyperbranched polyesters via a one-pot A₂ + B₃ esterification reaction. Intriguingly, the resultant hyperbranched polyesters carrying no conventional fluorescent units exhibited unexpected bright blue fluorescence under 365 nm UV light. It was found that the fluorescence intensity was enhanced with increasing solution concentrations and molecular weights of the polyesters. Moreover, the results suggested that the luminescence of polyesters could be controlled by solvents and metal ions. In particular, the fluorescence of the polyesters was extremely sensitive to Fe³⁺. More interesting is that the fluorescence of the polyesters showed an aggregation-induced enhanced emission in the mixture system. Notably, the resulting polyesters displayed a remarkably enhanced quantum yield (16.75%) as compared with that of other types of these polymers. Preliminary results demonstrate that clustering of the carbonyl groups is responsible for the unusual fluorescence in the aliphatic hyperbranched polyesters, namely, clustering-induced emission (CIE). This study provides a novel perspective for the design of biobased luminescent materials to new application areas.