Cucurbit[7]uril‐Encapsulation‐Controlled Supramolecular Photoproduct and Radical Fluorescence Emission

Herein, a host-guest interaction-controlled photoproduct created by using cucurbit[7]uril (Q[7])-based pseudorotaxane structures is reported. The assembly exhibited controlled behavior towards the reduction of the ethylene (C=C) bond in the tetrakis(pyridin-4-yl)ethylene (TPyE) guest molecule under UV light irradiation. This can be attributed to the Q[7] encapsulation masking the four pyridinium arms of the guest, which inhibits planarization of the TPyE core to form the cyclization product. In particular, the strong affinity of Q[7] for the butyl-substituted guest (TPyE-4C) led to an unusual radical fluorescence emission of the photoirradiation-triggered intermediate of the guest molecule being observed in aqueous solution. This work provides a valuable paradigm and new insight for macrocycle-based host-guest interactions in supramolecular catalysis and luminescent radical materials.