LAUSR

Supramolecular room temperature phosphorescence (RTP) materials are attractive due to their excellent RTP characteristics and water resistance. By evaluating the photophysical properties of HA/BisNpI‐doped materials, it is proved that hyaluronic acid (HA) is a promising matrix and the rigid plane N,N′‐(1,4‐phenylene)‐bis(1,8‐naphthalimide) (Ph‐BisNpI) is an excellent luminescent guest molecule for constructing RTP materials. Moreover, it is found that γ‐cyclodextrin (γ‐CD) can successfully bind BisNpI guest molecule. Accordingly, a tightly arranged ternary supramolecular system with HA as matrix, Ph‐BisNpI as the guest, and γ‐CD as the host is constructed by host‐guest interaction and hydrogen bonding. As expected, the obtained ternary supramolecular system HA/Ph@CD8 displays a superior RTP performance (52.7 ms longer lifetime than HA/Ph), water‐resistance, and even aqueous RTP (τ = 207 µs), which significantly extends the application of RTP in aqueous solution. These results are possibly attributed to the inclusion of γ‐CD on Ph‐BisNpI guest molecules and the self‐assembly of γ‐CD and HA to form a rigid hydrogen bonding network, which effectively inhibits the non‐radiative decay of Ph‐BisNpI and shields the triplet excitons from water and oxygen. Furthermore, the prepared ternary supramolecular RTP materials are successfully used as anticounterfeiting ink and exhibit broader application prospects in water environments.