Supramolecular Surface Engineering of Carbon Dots Enables Matrix‐Free Room Temperature Phosphorescence†

Comprehensive Summary Carbon dots (CDs) are an emerging class of nanomaterials with intriguing photophysical properties. Recently, achieving room temperature phosphorescence (RTP) for CDs has attracted considerable attention for biomedical and information applications. However, the CDs based RTP materials generally require the use of polymeric and inorganic matrix to provide the rigid environments, which remains a great challenge to obtain matrix‐free CDs with RTP. Herein, a novel supramolecular strategy based on strong interparticle interactions has been developed to attain this objective, by covalent decoration of ureido‐pyrimidinone (UPy, a multiple hydrogen bonding unit) on the surface of CDs. Structural characterizations validated the core‐shell structure of the as‐prepared CDs (EDTA‐CDs) and demonstrated the successful attachment of UPy via post‐modification (UPy‐CDs). The presence of UPy recognition units render the strong hydrogen bonding between UPy‐CDs, which stabilizes the triplet state via rigidifying effect. As a result, UPy‐CDs exhibit matrix‐free efficient RTP (λem = 534 nm) with high brightness and long lifetime (33.6 ms) in the solid state. Owing to the dual‐emission character, we further explored the application potential of UPy‐CDs in information encryption and anti‐counterfeiting. Overall, this work provides a new and facile strategy for achieving matrix‐free phosphorescent CDs with elegant incorporation of supramolecular chemistry.