Accurate Matching of a Secondary Amino-Functionality Metal-Organic Cage for Selective Recognition and Supramolecular Binding during Photoinduced Hydrogen Evolution.

Accurate matching of the active sites between the host and guest molecules has a great effect on the selective recognition of different but similar guest molecules or different binding abilities toward the same molecule. Herein, a pseudotetrahedral metal-organic cage (MOC, Co -TAP ) that contains secondary amino groups designed as guest-interacting sites was achieved. Co -TAP exhibits the selective recognition of uridine over other similar natural molecules via a fluorescent response. However, a reference structure (Co -TOP ) with the same configuration was also synthesized by replacing the secondary amine group with an oxygen atom of the ligand, and it reveals the selective recognition of guanosine. In addition, the accurate matching also enables Co -TAP to strongly bind the organic dye as a guest molecule via host-guest interactions, thus facilitating photoinduced electron transfer between the redox catalytic sites in MOC and the excited guest via a pseudointramolecular pathway.