Tunable Photoluminescence Properties of Microcrystalline Cellulose with Gradually Changing Crystallinity and Crystal Form

Abstract Nonconventional luminogens with persistent room temperature phosphoresce (p‐RTP) are attracting increasing attention owing to their momentous significance and diverse technical applications in optoelectronic and biomedical. So far, the p‐RTP emission of some amorphous powders or single crystals has been studied in depth. The p‐RTP emission of amorphous and fully crystalline states and their emission properties are widely divergent, while the difference of their p‐RTP emission mechanism is still controversial. The relevance between crystallinity change and p‐RTP properties is rarely studied. Furthermore, there is almost no research on the photoluminescence (PL) property change and emission mechanism under the crystal form transformation of semi‐crystalline polymer. Herein, microcrystalline cellulose (MCC) is chosen as a model compound to explore its crystallinity and the change in luminescence during the crystal form transformation to make up for this gap. By precisely adjusting the crystallinity and crystal cellulose conversion of MCC, the changing trend of quantum efficiency, and p‐RTP lifetime is consistent with the change of crystallinity, and the cellulose I may be more beneficial to PL emission than cellulose II. Clustering‐triggered emission mechanism can reasonably explain these interesting photophysical processes, which also can be supported by single‐crystal analysis and theoretical calculations.