Building a Green, Robust, and Efficient Bi-MOF Heterogeneous Catalyst for the Strecker Reaction of Ketones.

In this work, we present the new [Bi14(µ3-O)9(µ4-O)2(µ3-OH)5(3,5-DSB)5(H2O)3]·7H2O, BiPF-4 (bismuth polymeric framework─4) MOF, its microwave hydrothermal synthesis, as well as its behavior as a heterogeneous catalyst in the multicomponent organic Strecker reaction. The BiPF-4 material shows a three-dimensional (3D) framework formed by peculiar inorganic oxo-hydroxo-bismutate layers connected among them through the 3,5-dsb (3,5-disulfobenzoic acid) linker. These two-dimensional (2D) layers, built by junctions of Bi7 polyhedra SBU, provide the material of many Lewis acid catalytic sites because of the mixing in the metal coordination number. BiPF-4 is a highly robust, green, and stable material that demonstrates an excellent heterogeneous catalytic activity in the multicomponent Strecker reaction of ketones carried out in one-pot synthesis, bringing a reliable platform of novel green materials based on nontoxic and abundant metal sources such as bismuth.

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

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.

Vapor-Assisted Conversion of Heterobimetallic Titanium-Organic Framework Thin Films.

Heterobimetallic Metal-Organic Frameworks (MOFs) synergically combine the properties of two metal ions, thus offering significant advantages over homometallic MOFs in gas storage, separation, and catalysis, among other applications. However, these remain centered on bulk materials, while applications that require functional coatings on solid supports are not developed. We explore for the first time the deposition of heterometallic Ti-based MOF thin films using vapor-assisted conversion on substrates functionalized with a self-assembled monolayer. Furthermore, metal-induced dynamic topological transformation allows the conversion of MUV-10(Ca) films into MUV-101(Co) and MUV-102(Cu), which is not accessible through direct synthesis, without morphologically altering the films. These nonconventional thin-film deposition techniques enable homogeneous and crystalline coatings of heterometallic titanium MOFs that also maintain their corresponding porosity.