Visible-light harvesting pyrene-based MOFs as efficient ROS generators.

ABSTRACT: The utilization of reactive oxygen species (ROS) in organic transformations is of great interest due to their superior oxidative abilities under mild conditions. Recently, metal-organic frameworks (MOFs) have been developed as photosensitizers to transfer molecular oxygen to ROS for photochemical synthesis. However, visible-light responsive MOFs for oxygen activation remains scarce. Now we design and synthesize two porous MOFs, namely, PCN-822(M) (M = Zr, Hf), which are constructed by a 4,5,9,10-(K-region) substituted pyrene-based ligand, 4,4',4'',4'''-((2,7-di-tert-butylpyrene-4,5,9,10-tetrayl)tetrakis(ethyne-2,1-diyl))-tetrabenzoate (BPETB4-). With the extended ?-conjugated pyrene moieties isolated on the struts, the derived MOFs are highly responsive to visible light, possessing a broad-band adsorption from 225-650 nm. As a result, the MOFs can be applied as efficient ROS generators under visible-light irradiation, and the hafnium-based MOF, PCN-822(Hf), can promote the oxidation of amines to imines by activating molecular oxygen via synergistic photo-induced energy and charge transfer.

SUBMITTER: Zhang Y 

PROVIDER: S-EPMC6839506 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature