Toward Pore Size-Selective Photoredox Catalysis Using Bifunctional Microporous 2D Triazine-Based Covalent Organic Frameworks.

The design and synthesis of photoactive metal-free 2D materials for selective heterogeneous photoredox catalysis continue to be challenging due to issues related to nonrecyclability, and limited photo- and chemical stability. Herein, we report the photocatalytic properties of a triazine-based porous COF, , which is found to be capable of facilitating both SET (single electron transfer) for photocatalytic reductive debromination of phenacyl bromide in absence of oxygen and generation of reactive oxygen species (ROS) for benzylamine photo-oxidation in the presence of oxygen, respectively, under visible light irradiation. Inspired by the latter results, we further systematically investigated different-sized benzylamine substrates in this single-component reaction and compared the results with an analogous COF () exhibiting a larger pore size.

Polymer Connectivity Governs Electrophotocatalytic Activity in the Solid State.

The reductive functionalization of inert substrates like chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging approach to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is held back by the poor stability and mechanistic ambiguity of current homogeneous systems. Incorporating redox-active moieties into insoluble organic materials represents a promising strategy to unlock new heterogeneous catalytic activity while improving catalyst stability.

Redox-Active Organic Materials: From Energy Storage to Redox Catalysis.

Electroactive materials are central to myriad applications, including energy storage, sensing, and catalysis. Compared to traditional inorganic electrode materials, redox-active organic materials such as porous organic polymers (POPs) and covalent organic frameworks (COFs) are emerging as promising alternatives due to their structural tunability, flexibility, sustainability, and compatibility with a range of electrolytes. Herein, we discuss the challenges and opportunities available for the use of redox-active organic materials in organoelectrochemistry, an emerging area in fine chemical synthesis.

Structures of chloramphenicol acetyltransferase III and Escherichia coli β-ketoacylsynthase III co-crystallized with partially hydrolysed acetyl-oxa(dethia)CoA.

Acetyl coenzyme A (acetyl-CoA) is a reactive metabolite that nonproductively hydrolyzes in a number of enzyme active sites in the crystallization time frame. In order to elucidate the enzyme-acetyl-CoA interactions leading to catalysis, acetyl-CoA substrate analogs are needed. One possible analog for use in structural studies is acetyl-oxa(dethia)CoA (AcOCoA), in which the thioester S atom of CoA is replaced by an O atom.

Activity of Fatty Acid Biosynthesis Initiating Ketosynthase FabH with Acetyl/Malonyl-oxa/aza(dethia)CoAs.

Fatty acid and polyketide biosynthetic enzymes exploit the reactivity of acyl- and malonyl-thioesters for catalysis. A prime example is FabH, which initiates fatty acid biosynthesis in many bacteria and plants. FabH performs an acyltransferase reaction with acetyl-CoA to generate an acetyl--FabH acyl-enzyme intermediate and subsequent decarboxylative Claisen-condensation with a malonyl-thioester carried by an acyl carrier protein (ACP).

Emissive Substoichiometric Covalent Organic Frameworks for Water Sensing and Harvesting.

Emissive covalent organic frameworks (COFs) have recently emerged as next-generation porous materials with attractive properties such as tunable topology, porosity, and inherent photoluminescence. Among the different types of COFs, substoichiometric frameworks (so-called Type III COFs) are especially attractive due to the possibility of not only generating unusual topology and complex pore architectures but also facilitating the introduction of well-defined functional groups at precise locations for desired functions. Herein, the first example of a highly emissive (PLQY 6.

Catalytic Synthesis of Conjugated Azopolymers from Aromatic Diazides.

Conjugated polymers containing main chain azoarene repeat units are synthesized by a dinickel catalyzed N=N coupling reaction of aromatic diazides. The polymerization exhibits broad substrate scope and is compatible with heterocycles commonly featured in high performance organic materials, including carbazole, thiophene, propylenedioxythiophene (ProDOT), diketopyrrolopyrrole (DPP), and isoindigo. Copolymerizations can be carried out using monomer mixtures, and monoazide chain stoppers can be used to install well-defined end groups.