Search

Photoinduced metal-organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr-TPDCS-1, consisting of Zr 6 -clusters and TPDCS linkers (TPDCS=3,3'',5,5''-tetramercapto[1,1':4',1''-terphenyl]-4,4''-dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr 6 -cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram-scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl-radical catalysis., (© 2023 Wiley-VCH GmbH.)

Here we report the design of an enzyme-inspired metal-organic framework (MOF), 1 -OTf-Ir, by installing strong Lewis acid and photoredox sites in engineered mesopores. Al-MOF ( 1 ), with mixed 2,2'-bipyridyl-5,5-dicarboxylate (dcbpy) and 1,4-benzenediacrylate (pdac) ligands, was oxidized with ozone and then triflated to generate strongly Lewis acidic Al-OTf sites in the mesopores, followed by the installation of [Ir(ppy) 2 (dcbpy)] + (ppy = 2-phenylpyridine) sites to afford 1 -OTf-Ir with both Lewis acid and photoredox sites. 1 -OTf-Ir effectively catalyzed reductive cross-coupling of N -hydroxyphthalimide esters or aryl bromomethyl ketones with vinyl- or alkynyl-azaarenes to afford new azaarene derivatives. 1 -OTf-Ir enabled catalytic synthesis of anticholinergic drugs Pheniramine and Chlorpheniramine.

This concept paper aims to summarize recent research on the design and synthetic applications of metal‐organic frameworks (MOFs)‐based hydrogen atom transfer (HAT) catalysts. Functional MOFs have emerged as highly promising heterogeneous catalysts, leveraging their tunable, ordered structure and abundant active sites to enhance catalytic efficiency in various reactions. HAT, a versatile method for generating active open‐shell radical species through selective hydrogen abstraction, has been well explored in homogeneous photocatalysis. In contrast, heterogeneous HAT catalysis remains less developed, albeit their great potential in industry. This paper will provide a timely overview of the advancements in MOFs‐based HAT photocatalysis, classified according to catalytic centers including aromatic ketones, polyoxometalates, xanthene dyes, thiols, and alcohols, highlighting their design principles and practical applications in photocatalytic organic synthesis. [ABSTRACT FROM AUTHOR]

Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr‐TPDCS‐1, consisting of Zr6‐clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′‐tetramercapto[1,1′:4′,1′′‐terphenyl]‐4,4′′‐dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr6‐cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram‐scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl‐radical catalysis. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs), bridging metal‐containing second building units by organic ligands, have provided a versatile platform for the design of heterogeneous catalysis. In the last decade, various photo‐responsible MOFs have been designed and prepared, exhibiting outperformed catalytic performance. Among them, MOFs featuring organic photosensitizers for photoinduced organic transformations remain less investigated, due probably to the large steric demands and low symmetry of typical organic dyes. In view of the promising potential of integrating versatile MOFs with organic photosensitizers, this Concept summarizes recent advances in this research area. [ABSTRACT FROM AUTHOR]