Self-assembled cellulosic superstructures with unanticipated high quantum yields

Nonconventional luminophores devoid of traditional, large π-conjugates often suffer from low solid-state fluorescence quantum yields (FLQYs). In parallel, self-assembled bowl-shaped and helical architectures at the micro- and macroscale are unusual (mostly reported at the nanoscale). Here, we report that surface-stearoylated cellulose nanocrystals and cellulose stearoyl esters co-assemble into macroscale helices (FLQY: 86%) with diameters of 32-104 μm. Meanwhile, surface-lauroylated cellulose nanocrystals and cellulose lauroyl esters co-assemble into porous bowl-shaped microparticles (FLQY: 91%) with diameters of 8-19 μm. The high FLQYs are ascribed to the synergism of the dense oxygen clusters and abundant van der Waals interactions and hydrogen bonds between side stearoyl or lauroyl groups, which can promote through-space electron delocalization, ultimately improving fluorescence performance. These results were rationalized by theoretical calculations. Such superstructures exhibit great potential for stable anti-counterfeiting materials due to the excellent regeneration ability as well as structural stability of the oxygen clusters.