Assembly of a Heterometallic Cu(II)-Pd(II) Cage by Post-assembly Metal Insertion.

Porous structures based on multi-metallic motifs are receiving growing interest, but their general preparation still remains a challenge. Here, we report the self-assembly and structure of a Cu metal-organic cage (MOC) that is functionalized with free bis(pyrazolyl)methane sites. The homometallic CuL cage is isolated as a water-stable crystalline solid, and its formation is dependent on metal-ligand stoichiometry and the pre-organization of the Cu paddlewheel.

Linking metal-organic cages pairwise as a design approach for assembling multivariate crystalline materials.

Using metal-organic cages (MOCs) as preformed supermolecular building-blocks (SBBs) is a powerful strategy to design functional metal-organic frameworks (MOFs) with control over the pore architecture and connectivity. However, introducing chemical complexity into the network this route is limited as most methodologies focus on only one type of MOC as the building-block. Herein we present the pairwise linking of MOCs as a design approach to introduce defined chemical complexity into porous materials.

Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage.

The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry; however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized CuL lantern cage ().

Influence of the Synthesis and Storage Conditions on the Activity of Lipase B ZIF-8 Biocomposites.

The biomimetic mineralization of zeolitic imidazolate framework-8 (ZIF-8) has been reported as a strategy for enzyme immobilization, enabling the heterogenization and protection of biomacromolecules. Here, we report the preparation of different lipase B biocomposites (CALB@ZIF-8) formed by altering the concentrations of Zn and 2-methylimidazole (2-mIM). The influence of synthetic conditions on the catalytic activity of the lipase CALB was examined by hydrolysis and transesterification assays in aqueous and organic media, respectively.

MOF matrix isolation: cooperative conformational mobility enables reliable single crystal transformations.

Obtaining structural information for highly reactive metal-based species can provide valuable insight into important chemical transformations or catalytic processes. Trapping these metal-based species within the cavities of porous crystalline hosts, such as metal-organic frameworks (MOFs), can stabilise them, allowing detailed structural elucidation by single crystal X-ray diffraction. Previously, we have used a bespoke flexible MOF, [Mn3L2L'] (MnMOF-1, where L = bis-(4-carboxyphenyl-3,5-dimethylpyrazolyl)methane and L = L', but L' has a vacant N,N'-chelation site), which has a chelating site capable of post-synthetically binding metal ions, to study organometallic transformations and fundamental isomerisation processes.

A covalent deprotection strategy for assembling supramolecular coordination polymers from metal-organic cages.

A CuL metal-organic cage (MOC) composed of amine-protected ligands forms supramolecular coordination polymers (SCPs) upon covalent post-assembly deprotection. The amorphous SCPs form by virtue of aniline-copper coordination and possess a tunable porosity based on the rate of deprotection.

Impact of Higher-Order Structuralization on the Adsorptive Properties of Metal-Organic Frameworks.

The structural processing of metal-organic frameworks (MOFs) over multiple length scales is critical for their successful use as adsorbents in a variety of emerging applications. Although significant advances in molecular-scale design have provided strategies to boost the adsorptive capacities of MOFs, relatively little attention has been directed toward understanding the influence of higher-order structuralization on the material performance. Herein, we present the main strategies that are currently available for the structural processing of MOFs and discuss the influence these processes can impart on the adsorptive properties of the materials.