Thiadiazole-functionalized metal–organic frameworks for photocatalytic C–N and C–C coupling reactions: tuning the ROS generation efficiencyviacobalt introduction

Abstract

Heterogeneous photocatalytic organic transformations have attracted widespread attention due to their high efficiency, eco-friendliness, and atom economy. Herein, we report a cobalt-based metal–organic framework (JNU-207) constructed with a thiadiazole-functionalized photosensitizing...

Photoelectroactive metal–organic frameworks

“…Organic syntheses with selectivity for oxidation/reduction/cycloaddition reactions using photocatalysts are appealing. 46,248,249 These photocatalytic organic transformations include but are not limited to the oxidation of alcohols, 250,251 oxidation of amines, 75,[252][253][254][255][256] oxidation of suldes, 76,[257][258][259][260] reduction of nitroarenes, [261][262][263] C-C/C-N/C-halogen couplings, 78,251,256,259,264,265 Scheme 7 Representative phenolic compounds or phenols. Fig.…”

Linker Engineering for Reactive Oxygen Species Generation Efficiency in Ultra-Stable Nickel-Based Metal–Organic Frameworks

“…PCN-601 exhibits excellent alkali resistance and retains high crystallinity even in boiling NaOH solutions . Besides chemical stability, donor–acceptor (D–A)-type organic photosensitizers are commonly used in the construction of MOFs to promote charge separation and ROS generation. − For example, our group reported a Zn-based MOF ( JNU-204 ) constructed with a helical rod SBU and a D–A–D-type photosensitizer as the organic linker. JNU-204 exhibits significantly improved photocatalytic aerobic oxidation performance in three different types of organic transformations as opposed to other types of MOFs .…”

Mesoporous Mixed-Metal–Organic Framework Incorporating a [Ru(Phen)3]2+ Photosensitizer for Highly Efficient Aerobic Photocatalytic Oxidative Coupling of Amines

“…The development and full use of clean energy have been an essential research focus in recent decades. − Among many clean energy sources, sunlight is considered one of the best natural sources, and the organic transformation driven by visible light has successfully converted solar energy into chemical energy. − Under visible light irradiation with sufficiently high energy, a series of photoactivated chemical reactions could occur accompanied by the initiation of complex free radical mechanisms, so photocatalysis is widely viewed as a route to the green synthesis of some chemicals due to its environmental friendliness and high sustainability. − As the critical component of photocatalysis, a variety of materials have been explored and researched to induce electron–hole separation and promote photocatalytic organic transformation. However, the most efficient and practical visible-light-driven photocatalysts are still based mainly on the soluble complexes of noble metals with strong light absorption, such as Ru and Ir. − Several strategies for the utilization of the noble metal-based photocatalysts, including designing novel Ru/Ir complex-based molecular photosensitizers via the change of the ligand structure, loading small molecular photosensitizers onto different solid materials via electric adsorption, doping or deposition, and post-modifying metal ions on the skeleton of porous materials by coordination, have been developed. ,− Yet many unavoidable problems have to be faced on account of nonrecoverability, nonrecyclability, and scarcity for some expensive homogeneous photocatalysts, but poor interface contacts between phases, inefficient charge separation and transportation, uncontrollable load capacity, and deleterious semiconductor degradation side reactions for some heterogeneous photocatalysts. − Moreover, most reported photocatalysts can only be used for a specific reaction rather than the multireaction platform. − Therefore, it remains a huge challenge to develop efficient, recyclable, stable, and versatile photocatalysts nowadays.…”