Fully Exploiting Clusterization‐Triggered Room Temperature Phosphorescence of Cellulose by Stepwise Rigidification for Long‐Lived and Excitation Wavelength‐Dependent Afterglows

Abstract Achieving long‐lived room temperature phosphorescence (RTP) in nonconventional luminophores devoid of any conjugated units is fascinating but remains formidably challenging due to their low intersystem crossing efficiency and strong nonradiative decay. Herein, a stepwise rigidification strategy is developed to suppress the nonradiative decay and fully exploit the clusterization‐triggered RTP performance of cellulose. Specifically, the crystallinity is enhanced, and hydrogen bonding is reconstructed by a directed oxidation‐reduction reaction to afford a more rigid environment of cellulose; then, the reconstructed cellulose is further cross‐linked by boric acid to activate double confinement architecture. In return, the phosphorescence lifetime of the target cellulose increases almost one order of magnitude, and the phosphorescence quantum yield increases more than 27 folds. Moreover, the afterglow of the RTP cellulose can be regulated from blue to green by changing excitation wavelength, which is useful for advanced information encryption and anti‐counterfeiting. The stepwise rigidification strategy is also applicable for preparing other nature polysaccharides‐based long‐lived RTP materials, such as chitosan and sodium alginate. Nature polysaccharides are completely biodegradable; thus, this work paves the way for the development of eco‐friendly and practical color‐variable RTP materials.