Band Engineering of Benzothiadiazole‐Derived Metal‐Organic Frameworks for Photocatalytic Organic Transformations

ABSTRACT Metal‐organic frameworks (MOFs) have emerged as versatile platforms for photocatalysis, with their activity intrinsically governed by electronic structure. Parameters such as band alignment, redox potentials, and frontier orbital distributions regulate light absorption, charge separation efficiency, and interfacial reactivity. Among the available organic linkers, 2,1,3‐benzothiadiazole and its derivatives (BTID) have emerged as electron‐deficient building blocks that impart strong intramolecular charge‐transfer characteristics and tunable band structures. Incorporation of BTID units into MOF architectures improves visible‐light harvesting and extends excited‐state lifetimes, thereby enhancing photocatalytic efficiency. From a band‐structure‐oriented perspective, this review systematically discusses how linker design, metal node selection, and interfacial engineering collectively tailor the electronic properties of BTID‐based MOFs. Representative applications, including selective sulfoxidation, oxidative amine coupling, cross‐dehydrogenative coupling, and heterocycle synthesis, are analyzed to clarify mechanistic diversity. Density functional theory calculations and photoelectrochemical studies are integrated to establish clear correlations between structure, electronic properties, and catalytic performance, providing strategic guidance for the rational design of acceptor‐linker‐driven MOF photocatalysts.