Optical trapping-driven supramolecular photochirogenesis via higher-order complexation

Despite its potential, the optical trapping method has never been applied to supramolecular chemistry or chiral photochemistry. Here, we demonstrate that optical trapping using a focused laser beam boosts supramolecular assembly beyond the thermodynamic limitations and affords an unprecedented higher-order 2:4 complex through the otherwise-inaccessible dimerization of 1:2 complexes of g-cyclodextrin with two 2-anthracenecarboxylic acids (ACs). This process accelerates the chiral photocyclodimerization of ACs with switched regio-and enantio-selectivities. The combined use of opti-cal trapping and supramolecular photochirogenesis further enables the acquisition of photochemical snapshots of aggregation/disag-gregation behavior and enables the fate of a mixed aggregate generated at the laser focus to be tracked during and after optical trapping. This reveals that disaggregation requires >24 h to com-plete and shows that dimerization of 1:2 complexes is restricted in tightly packed aggregates but promoted in relaxing aggregates af-ter ceasing laser irradiation.