Vitrimers with covalent adaptable networks are a class of dynamic crosslinked polymers that can be reprocessed and self-repaired. However, their unitary functionality and poor responsiveness to external stimuli limit the potential of vitrimers for applications as smart materials. Herein, we proposed a new strategy by constructing an aggregation-induced emission (AIE)-active vitrimer (TER) via crosslinking epoxy derivatives of tetraphenylethylene to form a dynamic covalent network. The activated intramolecular rotation of AIEgen motifs with increasing temperature endows this vitrimer with thermal responsive photoluminescence. 1H static and 1H-13C wideline separation SSNMR experiments were used to investigate the molecular motion of the TER network, providing significant implications for the RIM mechanism of AIE in this AIE-active vitrimer. Moreover, as a dynamic crosslinked network, TER is a promising versatile material with excellent photoluminescence, reshaping, reprocessing and shape-memory properties. The AIE-active vitrimer not only represents a huge potential for further development of dynamic covalent polymers, but also extends the applications of vitrimers in different fields.

An AIE-active vitrimer is successfully synthesized through the crosslinking of epoxy derivatives of tetraphenylethylene. This vitrimer demonstrates photoluminescence and remarkable properties in terms of reshaping, reprocessing, and shape memory.