Supramolecular cuboctahedra with aggregation-induced emission enhancement and external binding ability

Beyond the AIE (aggregation-induced emission) phenomenon in small molecules, supramolecules with AIE properties have evolved in the AIE family and accelerated the growth of supramolecular application diversity. Inspired by its mechanism, particularly the RIV (restriction of intramolecular vibrations) process, a feasible strategy of constructing an AIE-supramolecular cage based on the oxidation of sulfur atoms and coordination of metals is presented. In contrast to previous strategies that used molecular stacking to limit molecular vibrations, we achieved the desired goal using the synergistic effects of coordination-driven self-assembly and oxidation. Upon assembling with zinc ions, S1 was endowed with a distinct AIE property compared with its ligand L1, while S2 exhibited a remarkable fluorescence enhancement compared to L2. Also, the single cage-sized nanowire structure of supramolecules was obtained via directional electrostatic interactions with multiple anions and rigid-shaped cationic cages. Moreover, the adducts of zinc porphyrin and supramolecules were investigated and characterized by 2D DOSY, ESI-MS, TWIM-MS, UV-vis, and fluorescence spectroscopy. The protocol described here enriches the ongoing research on tunable fluorescence materials and paves the way towards constructing stimuli-responsive luminescent supramolecular cages.