Guest-Regulated Generation of Reactive Oxygen Species from Porphyrin-Based Multicomponent Metallacages for Selective Photocatalysis.

The development of novel materials for highly efficient and selective photocatalysis is crucial for their practical applications. Herein, we employ the host-guest chemistry of porphyrin-based metallacages to regulate the generation of reactive oxygen species and further use them for the selective photocatalytic oxidation of benzyl alcohols. Upon irradiation, the sole metallacage (6) can generate singlet oxygen (1O2) effectively via excited energy transfer, while its complex with C70 (6⊃C70) opens a pathway for electron transfer to promote the formation of superoxide anion (O2⋅-), producing both 1O2 and O2⋅-. The addition of 4,4'-bipyridine (BPY) to complex 6⊃C70 forms a more stable complex (6⊃BPY) via the coordination of the Zn-porphyrin faces of 6 and BPY, which drives fullerenes out of the cavities and restores the ability of 1O2 generation. Therefore, benzyl alcohols are oxidized into benzyl aldehydes upon irradiation in the presence of 6 or 6⊃BPY, while they are oxidized into benzoic acids when 6⊃C70 is employed as the photosensitizing agent. This study demonstrates a highly efficient strategy that utilizes the host-guest chemistry of metallacages to regulate the generation of reactive oxygen species for selective photooxidation reactions, which could promote the utilization of metallacages and their related host-guest complexes for photocatalytic applications.

Hexaphenyltriphenylene-Based Multicomponent Metallacages: Host-Guest Complexation for White-Light Emission.

A hexaphenyltriphenylene-based hexatopic pyridyl ligand is designed and used to prepare three hexagonal prismatic metallacages via metal-coordination-driven self-assembly. Owing to the planar conjugated structures of the hexaphenyltriphenylene skeleton, such metallacages show good host-guest complexation with a series of emissive dyes, which have been further used to tune their emission in solution. Interestingly, based on their complementary emission colors, white light emission is achieved in a mixture of the host metallacages and the guests.

Hexaphenylbenzene-Based Deep Blue-Emissive Metallacages as Donors for Light-Harvesting Systems.

We herein report the preparation of a series of hexaphenylbenzene (HPB)-based deep blue-emissive metallacages via multicomponent coordination-driven self-assembly. These metallacages feature prismatic structures with HPB derivatives as the faces and tetracarboxylic ligands as the pillars, as evidenced by NMR, mass spectrometry and X-ray diffraction analysis. Light-harvesting systems were further constructed by employing the metallacages as the donor and a naphthalimide derivative (NAP) as the acceptor, owing to their good spectral overlap. The judiciously chosen metallacage serves as the antenna, providing the suitable energy to excite the non-emissive NAP, and thus resulting in bright emission for NAP in the solid state. This study provides a type of HPB-based multicomponent emissive metallacage and explores their applications as energy donors to light up non-emissive fluorophores in the solid state, which will advance the development of emissive metallacages as useful luminescent materials.