Framework Adaptability and Concerted Structural Response in a Bismuth Metal‐Organic Framework Catalyst.

Abstract

Bismuth metal-organic frameworks (MOFs) as heterogeneous catalysts are scarce, and there is little knowledge on the influence of the MOF features on their resulting activity and behavior. Here, we present the synthesis, characterization, and catalytic activity in the one-pot multicomponent Strecker reaction with ketones of three new MOFs prepared with the combination of indium or bismuth and 4,4',4'',4'''-methanetetrayltetrabenzoic acid. One of them, denoted BiPF-7, is very robust and chemically stable, and demonstrates a high activity in the formation of the desired α-aminonitriles. The interaction of the catalytic substrates with the metal centers in this MOF has been crystallographically characterized, showcasing a concerted framework adaptability process that involves structural changes in framework components that are not directly involved in the binding of the guests.

Two Zn(II)/Cd(II) Coordination Polymers as Recyclable Heterogeneous Catalysts for an Efficient Room-Temperature Synthesis of α-Aminonitriles via the Solvent-Free Strecker Reaction

“…Compared to the solvent-free, low catalytic loading, and room-temperature conditions used for 1a and 2a in this work, most of the heterogeneous catalysts for the Strecker reaction in the literature required the use of harsh conditions and high catalytic loadings (Table S5). − ,,, Selected examples from Table S5 are discussed further to elaborate these points. Certain In­(III)-based three-dimensional (3D) MOFs used for the reaction were found to be efficient at ambient temperature ranges with or without a solvent. ,− However, a Zr­(IV) 3D MOF afforded 100% conversion with 0.1 mol % catalyst loading at 50 °C .…”

“… − ,,, Selected examples from Table S5 are discussed further to elaborate these points. Certain In­(III)-based three-dimensional (3D) MOFs used for the reaction were found to be efficient at ambient temperature ranges with or without a solvent. ,− However, a Zr­(IV) 3D MOF afforded 100% conversion with 0.1 mol % catalyst loading at 50 °C . On the other hand, an EOSIN-Y-modified Zr­(IV) MOF provided 96% conversion with 0.3 mmol catalyst loading in 24 h using methanol as the solvent .…”

“…In view of this finding, metal complexes and metal oxides were tried as heterogeneous catalysts with easy separation and recyclability . Thus far, mostly indium (In)- and zirconium (Zr)-based MOFs/CPs were used as heterogeneous catalysts for the Strecker reaction in solvents, such as toluene, dichloromethane, and chloroform. − On the other hand, the d 10 metal-based MOFs/CPs have not been explored much. − Furthermore, no systematic study was conducted to evaluate the effect of UMCs on product yield. The preference for d 10 metal congeners, such as Zn­(II) and Cd­(II), lies in the fact that the variability in the coordination numbers in these two metal ions is a valuable tool for assessing the value of UMCs in such Lewis acid catalysis.…”

The Effect of Ligand-to-Metal Energy Transfer on the Photooxidation Performance of an Isostructural Series of Pyrene-Based Rare-Earth Metal–Organic Frameworks

“…[11][12][13] Within this realm, metal-organic frameworks (MOFs) are materials, often crystalline, comprised of metal ions, chains, or clusters interconnected by organic linkers, giving rise to highly porous structures. [14][15][16][17][18][19][20] MOFs are excellent candidates for heterogeneous catalysis for various reactions involving organic [21][22][23][24] or inorganic substrates. 25,26 The catalytic performance of MOFs is highly dependent on their mass transfer capability, which relies on pore aperture size, framework topology, and defects in the crystallite surface.…”

Bismuth gallate coordination networks inspired by an active pharmaceutical ingredient

“…1 Formulations such as bismuth subsalicylate and colloidal bismuth subcitrate (CBS) have mainly been used for their antimicrobial properties, such as in the treatment of Helicobacter pylori infections and other gastrointestinal disorders. 2–6 Recently, bismuth compounds have been shown to efficiently combat antibiotic resistant bacterial strains, 7 and are gaining interest as catalysts 8 for their low cost, as well as their non-toxic and non-corrosive nature. 9 Despite their large-scale production and long history of use, the structures of these materials have largely remained unknown or have only recently been determined.…”