This Concept paper summarizes the recent advances in metal-organic framework (MOF) based hydrogen atom transfer catalysis. Design principles, effects and advantages of MOF platform, and current limitations are discussed.

Abstract

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.