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

Abstract

The photochemical oxygenation reactions of a host−guest complex, pCp⊂[Ag 2 L0](SbF 6 ) 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 host−guest 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](SbF 6 ) 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⊂[Ag 2 L0](SbF 6 ) 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⊂[Ag 2 L1](SbF 6 ) 2 , possessing a mono-oxygenated C s -symmetrical macrocyclic skeleton.

Photooxidation-Driven Purely Organic Room-Temperature Phosphorescent Lysosome-Targeted Imaging

“…In particular, anthracene-involved photochemical reactions, which combines the merits of remote-controllable characteristics of light input and rich reactivity of diverse chemical products, have been drawn into the limelight and viewed as a classic and reliable means of conferring desired photoresponsiveness to supramolecular assembled architectures . In this context, many anthracene-derived building motifs, such as cyclodimers and endoperoxides, have been created to manipulate the molecular recognition properties of well-defined nanoconstructs . Also, anthryl groups can be employed as elongated π-aromatic cores to control topological structures and fluorescence emission behaviors .…”

Anthracene-Containing Metallacycles and Metallacages: Structures, Properties, and Applications

“…As a result, the phase-dependent reactivity and hostguest interactions have been disclosed. Specifically, the photosensitized oxygenation reaction of metallacycle resulted in the fully oxygenated product in solution, whereas a mono-oxygenated C s -symmetrical complex was provided in an amorphous solid state [84]. Our group introduced the reaction of a linear 9,10-bis(4-pyridyl)anthracene donor with a ~120 • Pt(II) complementary acceptor to prepare a hexagonal metallacycle via the [6 + 6] coordination-driven self-assembly.…”

Adaptive coordination assemblies based on a flexible tetraazacyclododecane ligand for promoting carbon dioxide fixation

“…7,8 Inspired by this, many unusual metal complexes which can be used to fix CO 2 through binding with carbonate have been reported. 9–13 Coordination-directed self-assembly has been proven to be an effective approach toward the predictable construction of multicomponent artificial hosts, 14–77 where enhanced guest reactivity, 73,74,78–87 stabilization of metastable species, 88–90 and unusual reaction pathways 78,91–94 have been realized. While atmospheric CO 2 sequestration by selective binding of carbonate with coordination hosts has already been reported, 95–102 adaptive coordination hosts that contain multiple active metal sites and can reversibly encapsulate and release the carbonate are still rare.…”