COFcap2, a recyclable tandem catalysis reactor for nitrogen fixation and conversion to chiral amines.

Two or more catalysts conducting multistep reactions in the same reactor, concurrent tandem catalysis, could enable (bio)pharmaceutical and fine chemical manufacturing to become much more sustainable. Herein we report that co-immobilization of metal nanoparticles and a biocatalytic system within a synthetic covalent organic framework capsule, COFcap-2, functions like an artificial cell in that, whereas the catalysts are trapped within 300-400 nm cavities, substrates/products can ingress/egress through ca. 2 nm windows.

Functional flexible adsorbents and their potential utility.

Physisorbents are poised to address global challenges such as CO capture, mitigation of water scarcity and energy-efficient commodity gas storage and separation. Rigid physisorbents, those adsorbents that retain their structures upon gas or vapour exposure, are well studied in this context. Conversely, cooperatively flexible physisorbents undergo long-range structural transformations stimulated by guest exposure.

A Needle in a Haystack: Transient Porosity in a Closed Pore Square Lattice Coordination Network.

Guest transport through discrete voids (closed pores) in crystalline solids is poorly understood. Herein, we report the gas sorption properties of a nonporous coordination network, [Co(bib)2Cl2]n·2MeOH (sql-bib-Co-Cl-α), featuring square lattice (sql) topology and the bent linker 1,3-bis(1H-imidazol-1-yl)benzene (bib). The as-synthesized sql-bib-Co-Cl-α has 11.

Green Synthesis of a New Schiff Base Linker and Its Use to Prepare Coordination Polymers.

Solid-state synthesis is an approach to organic synthesis that is desirable because it can offer minimal or no solvent waste, high yields, and relatively low energy footprints. Herein, we report the solid-state synthesis of a novel Schiff base, 4-{()-[(4-methylpyridin-3-yl)imino]methyl}benzoic acid (), synthesized through the reaction of an amine and an aldehyde. was prepared via solvent-drop (water) grinding (SDG) on a multigram scale with 97% yield and was characterized using FTIR, H NMR, and SCXRD.

An Ultramicroporous Physisorbent Sustained by a Trifecta of Directional Supramolecular Interactions.

2D and 3D porous coordination networks (PCNs) as exemplified by metal-organic frameworks, MOFs, have garnered interest for their potential utility as sorbents for molecular separations and storage. The inherent modularity of PCNs has enabled the development of crystal engineering strategies for systematic fine-tuning of pore size and chemistry in families of related PCNs. The same cannot be said about one-dimensional (1D) coordination polymers, CPs, which are understudied with respect to porosity.

Pimozide and Adipic Acid: A New Multicomponent Crystalline Entity for Improved Pharmaceutical Behavior.

Pimozide is a first-generation antipsychotic used in the treatment of schizophrenia, Gilles de la Tourette syndrome, and other chronic psychoses. Its in vivo efficacy is limited by poor solubility and consequent poor bioavailability. Therefore, adipic acid was used as a coformer for the preparation of a binary product with improved pharmaceutical properties.

Pore configuration control in hybrid azolate ultra-microporous frameworks for sieving propylene from propane.

Developing porous adsorbents for the complete sieving of propylene/propane mixtures represents an alternative method to energy-intensive cryogenic distillation processes. However, the similar physical properties of these molecules and the inherent trade-off among adsorption capacity, selectivity, diffusion kinetic and host-guest binding interactions in molecular sieving adsorbents makes their separation challenging. Here we report the separation of propylene/propane mixtures through a crystalline porous material (HAF-1) that features channels and shrinkage throats-the latter defined as narrower channels that connect the main channels and a molecular pocket-where the throat aperture is between the kinetic diameters of propylene and propane.

Crystal engineering of a new platform of hybrid ultramicroporous materials and their CH/CO separation properties.

Hybrid ultramicroporous materials (HUMs) comprised of combinations of organic and inorganic linker ligands are a leading class of physisorbents for trace separations involving C1, C2 and C3 gases. First generation HUMs are modular in nature since they can be self-assembled from transition metal cations, ditopic linkers and inorganic "pillars", as exemplified by the prototypal variant, SIFSIX-3-Zn (3 = pyrazine, SIFSIX = SiF ). Conversely, HUMs that utilise chelating ligands such as ethylenediamine derivatives are yet to be explored as sorbents.

Water sorption studies with mesoporous multivariate monoliths based on UiO-66.

Hierarchical linker thermolysis has been used to enhance the porosity of monolithic UiO-66-based metal-organic frameworks (MOFs) containing 30 wt% 2-aminoterephthalic acid (BDC-NH) linker. In this multivariate ( mixed-linker) MOF, the thermolabile BDC-NH linker decomposed at ∼350 °C, inducing mesopore formation. The nitrogen sorption of these monolithic MOFs was probed, and an increase in gas uptake of more than 200 cm g was observed after activation by heating, together with an increase in pore volume and mean pore width, indicating the creation of mesopores.

Exhaled Anesthetic Xenon Regeneration by Gas Separation Using a Metal-Organic Framework with Sorbent-Sorbate Induced-Fit.

Noble gas xenon (Xe) is an excellent anesthetic gas, but its rarity, high cost and constrained production prohibits wide use in medicine. Here, we have developed a closed-circuit anesthetic Xe recovery and reusage process with highly effective CO-specific adsorbent CUPMOF-5 that is promising to solve the anesthetic Xe supply problem. CUPMOF-5 possesses spacious cage cavities interconnected in four directions by confinement throat apertures of ~3.

Modulation of Water Vapor Sorption by Pore Engineering in Isostructural Square Lattice Topology Coordination Networks.

We report a crystal-engineering study conducted upon a platform of three mixed-linker square lattice () coordination networks of general formula [Zn(Ria)(bphy)] [bphy = 1,2-bis(pyridin-4-yl)hydrazine, HRia = 5-position-substituted isophthalic acid, and R = -Br, -NO, and -OH; compounds -]. Analysis of single-crystal X-ray diffraction data of - and the simulated crystal structure of revealed that - are isomorphous and sustained by bilayers of networks linked by hydrogen bonds. Although similar pore shapes and sizes exist in -, distinct isotherm shapes (linear and S shape) and uptakes (2.

Light and Guest Responsive Behavior in a Porous Coordination Network Enabled by Reversible [2+2] Photocycloaddition.

Stimuli-responsive physisorbents that undergo reversible structural transformations induced by external stimuli (e.g. light, guests, or heat) offer the promise of utility in gas storage and separation.

Gate-opening Induced by C8 Aromatics in a Double Diamondoid Coordination Network.

Coordination networks (CNs) that undergo guest-induced structural transformations are of topical interest thanks to their potential utility in separations and storage applications. Herein, we report a double diamondoid () topology CN, [Ni(bimpz)(bdc)(HO)] or (Hbdc = 1,4-benzenedicarboxylic acid, bimpz = 3,6-bis(imidazol-1-yl)pyridazine), that undergoes structural transformations induced by C8 isomers, i.e.

Effect of Polymorphism on the Sorption Properties of a Flexible Square-Lattice Topology Coordination Network.

The stimulus-responsive behavior of coordination networks (CNs), which switch between closed (nonporous) and open (porous) phases, is of interest because of its potential utility in gas storage and separation. Herein, we report two polymorphs of a new square-lattice () topology CN, , of formula [Cu(Imibz)] (HImibz = {[4-(1-imidazol-1-yl)phenylimino]methyl}benzoic acid), isolated from the as-synthesized CN , which subsequently transformed to a narrow pore solvate, , upon mild activation (drying in air or heating at 333 K under nitrogen). contains MeOH in cavities, which was removed through exposure to vacuum for 2 h, yielding the nonporous (closed) phase .

Dinuclear Copper Sulfate-Based Square Lattice Topology Network with High Alkyne Selectivity.

Porous coordination networks (PCNs) sustained by inorganic anions that serve as linker ligands can offer high selectivity toward specific gases or vapors in gas mixtures. Such inorganic anions are best exemplified by electron-rich fluorinated anions, e.g.

Insight into the Gas-Induced Phase Transformations in a 2D Switching Coordination Network via Coincident Gas Sorption and PXRD.

Switching coordination networks (CNs) that reversibly transform between narrow or closed pore (cp) and large pore (lp) phases, though fewer than their rigid counterparts, offer opportunities for sorption-related applications. However, their structural transformations and switching mechanisms remain underexplored at the molecular level. In this study, we conducted a systematic investigation into a 2D switching CN, [Ni(bpy)(NCS)], sql-1-Ni-NCS (1 = bpy = 4,4'-bipyridine), using coincident gas sorption and powder X-ray diffraction (PXRD) under low-temperature conditions.

Ethane/Ethylene Separations in Flexible Diamondoid Coordination Networks via an Ethane-Induced Gate-Opening Mechanism.

Separating ethane (CH) from ethylene (CH) is an essential and energy-intensive process in the chemical industry. Here, we report two flexible diamondoid coordination networks, and , that exhibit gate-opening between narrow-pore (NP) and large-pore (LP) phases for CH, but not for CH. thereby exhibited a type F-IV isotherm at 273 K with no CH uptake and a high uptake (111 cm g, 1 atm) for the NP and LP phases, respectively.

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity.

Hybrid ultramicroporous materials (HUMs), metal-organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, , incorporating the ligand (4-(3,5-dimethyl-1-pyrazol-4-yl)pyridine, ) and GeF pillaring anions.

Ultramicroporous Lonsdaleite Topology MOF with High Propane Uptake and Propane/Methane Selectivity for Propane Capture from Simulated Natural Gas.

Propane (CH) is a widely used fuel gas. Metal-organic framework (MOF) physisorbents that are CH selective offer the potential to significantly reduce the energy footprint for capturing CH from natural gas, where CH is typically present as a minor component. Here we report the CH recovery performance of a previously unreported lonsdaleite, , topology MOF, a chiral metal-organic material, [Ni(-IEDC)(bipy)(SCN)], .

Switching Adsorbent Layered Material that Enables Stepwise Capture of C Aromatics via Single-Crystal-to-Single-Crystal Transformations.

Separation of the C aromatic isomers, xylenes (PX, MX, and OX) and ethylbenzene (EB), is important to the petrochemical industry. Whereas physisorptive separation is an energy-efficient alternative to current processes, such as distillation, physisorbents do not generally exhibit strong C selectivity. Herein, we report the mixed-linker square lattice () coordination network [Zn(sba)(bis)]·DMF (, Hsba or = 4,4'-sulfonyldibenzoic acid, bis or = trans-4,4'-bis(1-imidazolyl)stilbene) and its C sorption properties.