Nature-Inspired Photocatalytic Azo Bond Cleavage with Red Light.

The emerging field of photoredox catalysis in mammalian cells enables spatiotemporal regulation of a wealth of biological processes. However, the selective cleavage of stable covalent bonds driven by low-energy visible light remains a great challenge. Herein, we report that red light excitation of a commercially available dye, abbreviated NMB+, leads to catalytic cleavage of stable azo bonds in both aqueous solutions and hypoxic cells and hence a means to photodeliver drugs or functional molecules. Detailed mechanistic studies reveal that azo bond cleavage is triggered by a previously unknown consecutive two-photon process. The first photon generates a triplet excited state, 3NMB+*, that is reductively quenched by an electron donor to generate a protonated NMBH•+. The NMBH•+ undergoes a disproportionation reaction that yields the initial NMB+ and two-electron-reduced NMBH (i.e., leuco-NMB, abbreviated as LNMB). Interestingly, LNMB forms a charge transfer complex with all four azo substrates that possess an intense absorption band in the red region. A second red photon induces electron transfer from LNMB to the azo substrate, resulting in azo bond cleavage. The charge transfer complex mediated two-photon catalytic mechanism reported herein is reminiscent of the flavin-dependent natural photoenzyme that catalyzes bond cleavage reactions with high-energy photons. The red-light-driven photocatalytic strategy offers a new approach to bioorthogonal azo bond cleavage for photodelivery of drugs or functional molecules.

Gold nanoclusters: Photophysical properties and photocatalytic applications.

Atomically precise gold nanoclusters (Au NCs) have high specific surface area and abundant unsaturated active sites. Traditionally, Au NCs are employed as thermocatalysts for multielectron transfer redox catalysis. Meanwhile, Au NCs also exhibit discrete energy levels, tunable photophysical and electrochemical properties, including visible to near infrared absorption, microsecond long-lived excited-state lifetime, and redox chemistry. In recent years, Au NCs are increasingly employed as visible to near infrared photocatalysts for their high photocatalytic activity and unique selectivity. This review focuses on the photophysical properties of a variety of Au NCs and their employment as photocatalysts in photocatalytic reactions and related applications including solar energy conversion and photodynamic therapies.