Phase-Dependent Reactivity and Host Guest Behaviors of a Metallo-Macrocycle in Liquid and Solid-State Photosensitized Oxygenation Reactions

The photochemical oxygenation reactions of a hostguest complex, pCp subset of[Ag(2)L0](SbF6)(2) (pCp = [2.2]paracyclophane) have been investigated in solution and in the solid state, using the macrocyclic ligand L0 having four anthracene moieties in the framework. As a result, it was found that the reactivity and hostguest functions show remarkable phase dependence. In solution, the photosensitized oxygenation of all the anthracene moieties of L0 resulted in a fully oxygenated macrocycle [Ag(2)L4](SbF6)(2) as the final product, while simultaneously the guest molecule was dissociated from the macrocyclic cavity. On the other hand, in an amorphous solid of pCp subset of[Ag(2)L0](SbF6)(2) prepared by decomposing single crystals through the removal of the crystalline solvent, the oxygenated site of L0 was significantly controlled to provide a site-selectively oxygenated inclusion complex, pCp subset of[Ag(2)L1](SbF6)(2), possessing a mono-oxygenated C-s-symmetrical macrocyclic skeleton.

Automated summary

The study investigated the photochemical oxygenation reactions of a host-guest complex in solution and in the solid state, showing remarkable phase dependence in reactivity and functions. The result revealed that in solution, the anthracene moieties of the ligand were fully oxygenated to form a macrocycle, while in the solid state, a site-selectively oxygenated inclusion complex was formed with controlled oxygenated sites.