Catalyst-free synthesis of diverse fluorescent polyoxadiazoles for the facile formation and morphology visualization of microporous films and cell imaging

Abstract

The development of facile polymerizations toward functional heterocyclic polymers is of great significance for chemistry and materials science. As an important class of heterocyclic polymers, polyoxadiazoles (PODs) have found applications in various fields. However, the synthetic difficulties of PODs greatly restrict their structural diversity and property investigation. Herein, we report a series of catalyst-free multicomponent polymerizations (MCPs) that can facilely synthesize functional PODs with well-defined and diversified topological structures from commercially available or readily accessible aldehydes, carboxylic acids, secondary amines, and (N-isocyanimino)triphenylphosphorane at room temperature. Unlike conventional Ugi polycondensations, the present Ugi-type MCPs can in situ generate oxadiazole moieties in polymer backbones. The obtained PODs possess good solubility, high thermal and morphological stability, and excellent film-forming ability. The introduction of aggregation-induced emission (AIE) moieties together with the inherent structural features of PODs endow these polymers with multiple functionalities. The AIE-active linear PODs can form fluorescent microporous films with stable and ordered structures based on the simple breath figure patterning method, and the self-assembly morphologies can be directly visualized by fluorescence microscopy in a high-contrast and sensitive manner. Moreover, both the linear and hyperbranched AIE-active PODs possess excellent biocompatibility, good lysosome specificity, and excellent photobleaching resistance, which enable them to serve as promising lysosome-specific fluorescent probes in biological imaging.