Primary Amine-Functionalized Chiral Covalent Organic Framework Enables High-Efficiency Asymmetric Catalysis in Water.

Aqueous asymmetric catalysis using chiral covalent organic frameworks (COFs) represents a significant advancement but remains to be explored. Herein, we present the first example of aqueous asymmetric catalysis catalyzed by a primary amine-tagged chiral -ADP-TAPB COF. The -ADP-TAPB COF was synthesized by the postsynthetic deprotection of -ADP-TAPB-Boc bearing a protective tert-butoxycarbonyl (Boc) group, which was constructed by a Schiff-base reaction between an alanine-derived chiral building block (-ADP-Boc) and 1,3,5-tris(4-aminophenyl)benzene (TAPB).

Structural Comparisons, Fluorescence Properties, and Glass-to-Crystal Transformations of Heat-Cooled and Melt-Quenched Zeolitic Imidazolate Framework Glass.

As a representative of zeolitic imidazolate framework glass, agZIF-62 has been reported to be synthesized using a melt-quenching method in which the ZIF-62 crystal is heated to a temperature above the melting point. Interestingly, we unexpectedly found that agZIF-62 can also be synthesized by simple heating at temperatures lower than the melting point, which may be assisted by the release of encapsulated solvent molecules. The structural differences between melt-quenched agZIF-62 (MQ-agZIF-62) and heat-cooled agZIF-62 (HC-agZIF-62) were investigated.

Construction of binary metal-organic cage-based materials a "covalently linked plus cage encapsulated" strategy.

A strategy for constructing binary metal-organic cage (MOC)-based materials was developed. The cationic MOCs were covalently linked by organic linkers to a cationic extended network, whereas the anionic MOCs acted as counterions and were encapsulated in the network. Compared with the corresponding unary materials, the binary MOC-based materials exhibited improved porosity and adsorption performance.

Construction of a Defective Chiral Covalent Organic Framework for Fluorescence Recognition of Amino Acids.

The design and synthesis of chiral covalent organic frameworks (COFs) with controlled defect sites are highly desirable but still remain largely unexplored. Herein, we report the synthesis of a defective chiral HD-TAPB-DMTP COF by modifying the chiral monomer helicid (HD) into the framework of an achiral imine-linked TAPB-DMTP COF using a chiral monomer exchange strategy. Upon the introduction of the chiral HD unit, the obtained defective chiral HD-TAPB-DMTP COF not only displays excellent crystallinity, large specific surface area (up to 2338 m/g) and rich accessible chiral functional sites but also exhibits fluorescence emission, rendering it a good candidate for discrimination of amino acids.

Metal-organic framework derived heterostructured phosphide bifunctional electrocatalyst for efficient overall water splitting.

Developing high active and stable cost-effective bifunctional electrocatalysts for overall water splitting to produce hydrogen is of vital significance in clean and sustainable energy development. This work has prepared a novel porous unreported MOF (Ni-DPT) as a precursor to successfully synthesize a non-noble bifunctional NiCoP/NiP@NF electrocatalyst through doping strategy and interface engineering. This catalyst is constructed by layered self-supporting arrays with heterojunction interface and rich nitrogen-phosphorus doping.

Hierarchical porous amorphous metal-organic frameworks constructed from ZnO/MOF glass composites.

For the first time, hierarchical porous amorphous metal-organic frameworks (HP-aMOFs) containing ultramicropores, micropores, and mesopores were synthesized by etching a composite of MOF glass (agZIF-76) and ZnO using ammonia. These materials show potential applications in the adsorption of C2 hydrocarbons.

Raising the Asymmetric Catalytic Efficiency of Chiral Covalent Organic Frameworks by Tuning the Pore Environment.

Chiral covalent organic frameworks (COFs) hold considerable promise in the realm of heterogeneous asymmetric catalysis. However, fine-tuning the pore environment to enhance both the activity and stereoselectivity of chiral COFs in such applications remains a formidable challenge. In this study, we have successfully designed and synthesized a series of clover-shaped, hydrazone-linked chiral COFs, each with a varying number of accessible chiral pyrrolidine catalytic sites.

Iodine Adsorption-Desorption-Induced Structural Transformation and Improved Ag Turn-On Luminescent Sensing Performance of a Nonporous Eu(III) Metal-Organic Framework.

Posttreatment of pristine metal-organic frameworks (MOFs) with suitable vapor may be an effective way to regulate their structures and properties but has been less explored. Herein, we report an interesting example in which a crystalline nonporous Eu(III)-MOF was transferred to a porous amorphous MOF (aMOF) via iodine vapor adsorption-desorption posttreatment, and the resulting aMOF showed improved turn-on sensing properties with respect to Ag ions. The crystalline Eu-MOF, namely, Eu-IPDA, was assembled from Eu(III) and 4,4'-{4-[4-(1-imidazol-1-yl)phenyl]pyridine-2,6-diyl}dibenzoic acid (HIPDA) and exhibited a two-dimensional (2D) coordination network based on one-dimensional secondary building blocks.

Tuning the Topology of Two-Dimensional Covalent Organic Frameworks through Site-Selective Synthetic Strategy.

Tuning the topology of two-dimensional (2D) covalent organic frameworks (COFs) is of paramount scientific interest but remains largely unexplored. Herein, we present a site-selective synthetic strategy that enables the tuning of 2D COF topology by simply adjusting the molar ratio of an amine-functionalized dihydrazide monomer (NH -Ah) and 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (Tz). This approach resulted in the formation of two distinct COFs: a clover-like 2D COF with free amine groups (NH -Ah-Tz) and a honeycomb-like COF without amine groups (Ah-Tz).

Porous amorphous metal-organic frameworks based on heterotopic triangular ligands for iodine and high-capacity dye adsorption.

The research on amorphous metal-organic frameworks (aMOFs) is still in its infancy, and designing and constructing aMOFs with functional pores remains a challenge. Two aMOFs based on Co(II) and heterotopic triangular ligands with large conjugated aromatic planes, namely aMOF-1 and aMOF-2, were constructed and characterized by IR, XPS, EA, ICP, XANS and so on. aMOF-1 possesses mesopores, whereas aMOF-2 possesses micropores.

Encapsulation of a metal-organic cage-based porous salt in silica nanopores.

A metal-organic cage (MOC)-based porous salt composed of cationic Zr-MOC and anionic Cu-MOC was incorporated into SBA-15 nanopores a two-step impregnation method for the first time. The encapsulated MOC-based porous salt showed improved iodine adsorption capacity when compared with the bulk sample.

A mixed-ligand Co(II) MOF synthesized from a single organic ligand to capture iodine and methyl iodide vapour.

Mixed-ligand metal-organic frameworks (MOFs) are usually synthesized from two or more organic ligands as initial reactants, and MOFs synthesized from one organic ligand precursor through partial reactions remain very limited. Herein, by introducing an imidazole-tetrazole bifunctional ligand, 5-(4-imidazol-1-yl-phenyl)-2-tetrazole (HIPT), as a single ligand and performing hydrolysis of the tetrazolium group, a mixed-ligand Co(II)-MOF based on HIPT and 4-imidazol-1-yl-benzoic acid (HIBA), [Co(μ-O)(IPT)(IBA)]· solvent (Co-IPT-IBA), was constructed and applied to capture I and methyl iodide vapours. Single crystal structural analyses reveal that Co-IPT-IBA exhibits a 3D porous framework with 1D channels based on the relatively few reported ribbon-like rod SBUs.

Postmodification of an Amine-Functionalized Covalent Organic Framework for Enantioselective Adsorption of Tyrosine.

The development of chiral covalent organic frameworks (COFs) by postsynthetic modification is challenging due to the common occurrences of racemization and crystallinity decrement under harsh modification conditions. Herein, we employ an effective site-selective synthetic strategy for the fabrication of an amine-functionalized hydrazone-linked COF, NH-Th-Tz COF, by the Schiff-base condensation between aminoterephthalohydrazide (NH-Th) and 4,4',4″-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (Tz). The resulting NH-Th-Tz COF with free amine groups on the pore walls provides an appealing platform to install desired chiral moieties through postsynthetic modification.

Metal-organic framework derived FeNi alloy nanoparticles embedded in N-doped porous carbon as high-performance bifunctional air-cathode catalysts for rechargeable zinc-air battery.

Developing efficient and durable bifunctional air-cathode catalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the key efforts promoting the practical rechargeable zinc-air batteries (ZABs). In this paper, high-performance bifunctional air-cathode catalysts by a two-step strategy: atomically dispersed Ni on N-doped carbon is first derived from MOF to form uniformly dispersed NiNC, which are pyrolyzed together with Fe source at different high-temperatures to form FeNi@NC-T (T = 800, 900, and 1000 °C) catalysts. The as-synthesized non-noble metal FeNi@NC-900 catalyst exhibits a considerably small potential gap (ΔE) of 0.

Self-Assembly of Helical Nanofibrous Chiral Covalent Organic Frameworks.

Despite significant progress on the design and synthesis of covalent organic frameworks (COFs), precise control over microstructures of such materials remains challenging. Herein, two chiral COFs with well-defined one-handed double-helical nanofibrous morphologies were constructed via an unprecedented template-free method, capitalizing on the diastereoselective formation of aminal linkages. Detailed time-dependent experiments reveal the spontaneous transformation of initial rod-like aggregates into the double-helical microstructures.

Regulating the Porosity and Iodine Adsorption Properties of Metal-Organic Framework Glass via an Ammonia-Immersion Approach.

Metal-organic framework (MOF) glass is a new type of glass material, but it usually lacks sufficient porosity. Thus, regulating the pore structure of MOF glass to improve its adsorption performance is very important. Herein, we found that the porosity of MOF glasses agZIF-62 and agZIF-76 can be regulated via an ammonia-immersion approach.

Strategies for the Construction of Functional Materials Utilizing Presynthesized Metal-Organic Cages (MOCs).

Metal-organic cages (MOCs) that assemble from metal ions or metal clusters and organic ligands have attracted the interest of the scientific community because of their various functional coordination cavities. Unlike metal-organic frameworks (MOFs) with infinite frameworks, MOCs have discrete structures, making them soluble and stable in certain solvents and facilitating their application as starting reagents in the further construction of single components or composite materials. In recent years, increasing progress has been made in this field.

Fabrication of cellulose derivative coated spherical covalent organic frameworks as chiral stationary phases for high-performance liquid chromatographic enantioseparation.

Porous spherical silica-based chiral stationary phases (CSPs) have been commercially used in the field of chiral separation, however, the scope of their application is, to some extent, limited by the instability of silica towards mobile phase containing strong base or acid. As such, developing new matrix-based CSPs is one of the effective strategies to overcome this bottleneck in studies of chiral separation materials. In this work, we have demonstrated that stable spherical covalent organic frameworks (SCOFs) can be utilized as matrixes for the fabrication of new CSPs for the first time.

Facile and Site-Selective Synthesis of an Amine-Functionalized Covalent Organic Framework.

Amine-functionalized covalent organic frameworks (COFs) hold great potential in diversified applications. However, the synthesis is dominated by postsynthetic modification, while the de novo synthesis allowing for direct installation of amine groups remains a formidable challenge. Herein, we develop a site-selective synthetic strategy for the facile preparation of amine-functionalized hydrazone-linked COF for the first time.

Amorphous metal-organic frameworks obtained from a crystalline precursor for the capture of iodine with high capacities.

Two amorphous metal-organic frameworks (MOFs) were obtained from crystalline Co-MOF (SCNU-Z6) temperature-induced (-SCNU-Z6) and water-immersed (-SCNU-Z6) approaches. They exhibited high iodine uptake, with the adsorption capacities of -SCNU-Z6 and -SCNU-Z6 reaching 2.05 and 5.

Degradation pathways of penthiopyrad by δ-MnO mediated processes: a combined density functional theory and experimental study.

Penthiopyrad is a widely used succinate dehydrogenase inhibitor (SDHI) fungicide and frequently detected in natural environments. In order to better understand its fate in natural systems, the degradation of penthiopyrad by manganese dioxide (MnO) was investigated in this study. The results show that penthiopyrad is rapidly degraded in the δ-MnO system.

Covalent Cross-Linking of Metal-Organic Cages: Formation of an Amorphous Cationic Porous Extended Framework for the Uptake of Oxo-Anions from Water.

Invited for this month's cover are the collaborating groups of Sheng-Run Zheng and Wei-Guang Zhang from South China Normal University, China. The cover picture shows an amorphous cationic porous metal-organic material that constructed from the covalent linking of large cationic metal-organic cage for the removal of toxic oxo-anions from water with high capacities and rapid kinetics. Read the full text of the article at 10.

Covalent Cross-Linking of Metal-Organic Cages: Formation of an Amorphous Cationic Porous Extended Framework for the Uptake of Oxo-Anions from Water.

Cationic amorphous metal-organic cage (MOC)-based materials capable of removing anionic pollutants from water are receiving increasing attention but they are still relatively less reported. Herein, for the first time, a cationic porous MOC-based extended framework, namely, CL-aMOC-1, was constructed by covalent linking of a cationic Pd L (L=3,5-di-pyridin-4-yl-benzaldehyde) cage with a 1,4-bis(4-aminophenyl)benzene (BAPB) linker. Interestingly, the reaction could be completed within 15 min using an amorphous MOC-based solid (aMOC-1) and BAPB as reactant via a low-temperature solid-state reaction.

A Mn(II)-MOF with inherent missing metal-ion defects based on an imidazole-tetrazole tripodal ligand and its application in supercapacitors.

A metal-organic framework (MOF), namely SCNU-Z3, based on an imidazole-tetrazole tripodal ligand and Mn(ii), has been constructed. It exhibits a porous 3D framework composed of truncated octahedron cage subunits. Unexpected ligand-induced missing metal-ion defects were observed in the framework.