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Amine modified Zr6-based metal–organic frameworks (MOFs) were synthesized through solvent-assisted linker incorporation (SALI) and utilized as single-component heterogeneous catalysts for the hydrolysis of organophosphorous compounds under solely aqueous conditions at room temperature. These materials display unprecidentedly fast catalytic hydrolysis for dimethyl p-nitrophenyl phosphate (DMNP) and nerve agent VX without the use of a buffered solution. [ABSTRACT FROM AUTHOR]

Herein we demonstrate the use of host–guest chemistry to modulate rates of charge transport in metal–organic framework (MOF) films. The kinetics of site-to-site of charge hopping and, in turn, the overall redox conductivity, of a ferrocene-modified MOF can be altered by up to 30-fold by coupling electron exchange to the oxidation-state-dependent formation of inclusion complexes between cyclodextrin and channel-tethered metallocenes. [ABSTRACT FROM AUTHOR]

Uniform thin films of a metal–organic framework, which is constructed from free-base porphyrin linkers and hexa-zirconium nodes (MOF-525), are solvothermally grown on conducting substrates. Subsequently, solvothermal post metalations are employed to prepare the Zn-MOF-525 and Co-MOF-525 thin films. All the thin films are electroactive in aqueous media. [ABSTRACT FROM AUTHOR]

Thermal treatment of highly stable porous organic polymersbased upon the Yamamoto polymerization of 2,2′,7,7′-tetrabromo-9,9′-spirobifluorenewas done. The polymers are shown to be thermally and chemically stable.Upon thermal treatment the polymers are shown to have BET surfaceareas of ca. 2,000 m2/g and 2,500 m2/g respectively. [ABSTRACT FROM AUTHOR]

We have synthesized, characterized, and computationally simulated/validated the behavior of two new metal-organic framework (MOF) materials displaying the highest experimental Brunauer-Emmett-Teller (BET) surface areas of any porous materials reported to date (7000 m2/g). Key to evacuating the initially solvent-filled materials without pore collapse, and thereby accessing the ultrahigh areas, is the use of a supercritical CO2 activation technique. Additionally, we demonstrate computationally that by shifting from phenyl groups to "space efficient" acetylene moieties as linker expansion units, the hypothetical maximum surface area for a MOF material is substantially greater than previously envisioned (14600 m2/g (or greater) versus 10500 m2/g). [ABSTRACT FROM AUTHOR]

We have synthesized, characterized, and computationally validated the high Brunauer—Emmett—Teller surface area and hydrogen uptake of a new, noncatenating metal—organic framework (MOF) material, NU-III. Our results imply that replacing the phenyl spacers of organic linkers with triple-bond spacers is an effective strategy for boosting molecule-accessible gravimetric surface areas of MOFs and related high-porosity materials. [ABSTRACT FROM AUTHOR]

Robust catechol-functionalized porous organic polymers(POPs) withtunable porosities (560–1050 m2/g) and degrees offunctionalization were synthesized using a cobalt-catalyzed acetylenetrimerization (CCAT) strategy. Post-synthesis metalation canbe readily carried out with a wide range of metal precursors (CuII, MgII, and MnIIsalts and complexes),resulting in metalated POPs with enhanced heat of hydrogen adsorptionscompared to the starting nonmetalated materials. [ABSTRACT FROM AUTHOR]

Two noninterpenetrated MOFs with strikingly differentstructures, NU-108-Cuand NU-108-Zn, wereprepared from asingle hexa-carboxylated ligand. NU-108-Cucontains paddlewheel-coordinatedcopper ions as nodes and is based on a 3,24 network associated withan inherently noncatenating rht-topology. Modificationsintroduced in the hexa-carboxylated struts (uniquely placed phenylspacers) lead to substantial changes in pore sizes, relative to thosefound in other MOFs based on 3,24 networks and paddlewheel-coordinatedcopper ions. NU-108-Znfeatures a new net based on (3,3,6)-connecterand octadehral Zn4O nodes in which all struts lie in a–bplanes. [ABSTRACT FROM AUTHOR]

A pillared-paddlewheel type metal-organic framework material featuring bodipy- and porphyrin-based struts, and capable of harvesting light across the entire visible spectrum, has been synthesized. Efficient-essentially quantitative-strut-to-strut energy transfer (antenna behavior) was observed for the well-organized donor-acceptor assembly consituting the ordered MOF structure. [ABSTRACT FROM AUTHOR]

A new class of infinite coordination polymers (CP) was synthesized using a tetrahedral tetrakis[4-(4′-phenyl-2,2′:6′,2′′-terpyridine)phenyl]methane ligand as an organic node to direct the three-dimensional growth of the network and MII(M = Zn, Fe, Ni, and Ru) ions as inorganic linkers, an approach that is the opposite of the metal-as-a-node strategy used in the construction of metal–organic frameworks (MOFs). The unusual rod-like morphology of the resulting microporous materials can be tuned viasolvents and reaction conditions. The covalent entrapment of a [Ru(tpy)2]2+moiety in the skeleton of the 3D-network enables the Ru-CP to exhibit room-temperature luminescence. [ABSTRACT FROM AUTHOR]

On account of their structural similarity to cofactors found in many metallo-enzymes, metalloporphyrins are obvious potential building blocks for catalytically active, metal-organic framework (MOF) materials. While numerous porphyrin-based MOFs have already been described, versions featuring highly accessible active sites and permanent microporosity are remarkably scarce. Indeed, of the more than 70 previously reported porphyrinic MOFs, only one has been shown to be both permanently microporous and contain internally accessible active sites for chemical catalysis. Attempts to generalize the design approach used in this single successful case have failed. Reported here, however, is the synthesis of an extended family of MOFs that directly incorporate a variety of metalloporphyrins (specifically Al3+, Zn2+, Pd2+, Mn3+, and Fe3+ complexes). These robust porphyrinic materials (RPMs) feature large channels and readily accessible active sites. As an illustrative example, one of the manganese-containing RPMs is shown to be catalytically competent for the oxidation of alkenes and alkanes. [ABSTRACT FROM AUTHOR]

Abstract: Two new metal–organic framework (MOF) materials based on boron-rich cluster struts (p-carborane) are reported herein. Cu(I) catalyzed coupling chemistry was used to synthesize carboxylate-based ligands, which are substantially longer than the previously studied dicarboxylated p-carborane, leading to structures with greater porosity. Solvothermal syntheses involving these ligands and Zn salts were used to prepare two new Zn(II)-based MOFs with 2D and 3D open framework structures. Upon thermal activation, these MOFs retain the chemical identity of their frameworks, leading to highly porous materials. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks-a class of porous hybrid materials built from metal ions and organic bridges-have recently shown great promise for a wide variety of applications. The large choice of building blocks means that the structures and pore characteristics of the metal-organic frameworks can be tuned relatively easily. However, despite much research, it remains challenging to prepare frameworks specifically tailored for particular applications. Here, we have used computational modelling to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area. Subsequent experimental synthesis yielded a material, matching the calculated structure, with a high BET surface area (6,143 m2 g−1). Furthermore, sorption measurements revealed that the material had high storage capacities for hydrogen (164 mg g−1) and carbon dioxide (2,315 mg g−1)-gases of high importance in the contexts of clean energy and climate alteration, respectively-in excellent agreement with predictions from modelling. [ABSTRACT FROM AUTHOR]

Carboranes represent a potentially rich but underutilized class of inorganic and catabolism-inert pharmacophores. The regioselectivity and ease of derivatization of carboranes allows for facile syntheses of a wide variety of novel structures. The steric bulk, rigidity, and ease of B- and C-derivatization and lack of π-interactions associated with hydrophobic carboranes may be exploited to enhance the selectivity of previously identified bioactive molecules. Transthyretin (TTR) is a thyroxine-transport protein found in the blood that has been implicated in a variety of amyloid related diseases. Previous investigations have identified a variety of nonsteroidal antiinflammatory drugs (NSAID5) and structurally related derivatives that imbue kinetic stabilization to TTR, thus inhibiting its dissociative fragmentation and subsequent aggregation to form putative toxic amyloid fibrils. However, the cyclooxygenase (COX) activity associated with these pharmaceuticals may limit their potential as long-term therapeutic agents for TTR amyloid diseases. Here, we report the synthesis and evaluation of carborane-containing analogs of the promising NSAID pharmaceuticals previously identified. The replacement of a phenyl ring in the NSAIDs with a carborane moiety greatly decreases their COX activity with the retention of similar efficacy as an inhibitor of TTR dissociation. The most promising of these compounds, 1-carboxylic acid-7-[3-fluorophenyl]-1,7-dicarba-closo-dodecaborane, showed effectively no COX-1 or COX-2 inhibition at a concentration more than an order of magnitude larger than the concentration at which TTR dissociation is nearly completely inhibited. This specificity is indicative of the potential for the exploitation of the unique properties of carboranes as potent and selective pharmacophores. [ABSTRACT FROM AUTHOR]

Abstract: A novel homotrifunctional conjugation reagent, 1,3,5-tris-(N-maleimidomethyl)benzene has been synthesized in high yield with minimum purification. The reactivity of this compound was examined by using l-cysteine as a nucleophile. [Copyright &y& Elsevier]

The scope and limitations of the alkylation of [closo-B12(OH)12]2- using a series of fourteen alkyl and aralkyl halides and two p-toluenesulfonic acid esters in the presence of N,N-diisopropylethylamine have been investigated. The dodecaalkoxy-closo-dodecaborate products, [closo-B12(OR)12]2-, and their hypercloso two-electron oxidation products have been explored. The species [closoB12(OR)12]2- containing 26 cage-bonding electrons may undergo two reversible, sequential, one-electron oxidation processes, producing a 25-electron radical anion and a 24-electron neutral species. Several oxidizing reagents were investigated for the chemical oxidation of [closo-B12(OR)12]2- and [hypercloso-B12(OR)12] to [hypercloso-B12(OR)12]. Both FeCl3.6H2O and K3Fe(CN)6 in 90/5/5 ethanol/acetonitrile/H2O were found to be the reagents of choice. The reverse reaction leading from the neutral species to the radical anion and subsequently to the dianion was achieved using sodium borohydride in ethanol. A variety of alkoxyl derivatives have been synthesized by heating the reactants for extended periods of time in acetonitrile at the ref lux temperature. The use of elevated reaction temperatures attained by employing moderate argon pressure (autoclave) over the reaction mixture led to drastic reductions in reaction times and increased efficiency. X-ray diffraction studies of substituted dodecabenzyl ether derivatives proved that 22- has approximate ln symmetry while hypercloso-2, -3, -9, -11, -12, and -13 have approximate D3d point group symmetry due to Jahn-Teller distortion from ln. [ABSTRACT FROM AUTHOR]

Four metalloporphyrinic metal–organic frameworks (MOFs) were successfully synthesized and exhibited enhanced activities for the photooxidation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Among them, a Sn-porphyrin functionalized 2D MOF, namely CSLA-21-NH2(Sn), showed a half-life of 1.5 min for CEES oxidation under blue LED, featuring as one of the fastest photocatalysts for CEES degradation. [ABSTRACT FROM AUTHOR]

MXenes, a novel class of 2D materials, exhibit great potential for energy storage due to their unique layered structure and excellent electrical conductivity. However, improving the intrinsic electrochemical storage capacity of MXenes remains a significant challenge, often requiring the incorporation of other Faradaic materials. Oxidation, in particular, poses a key issue that impacts the capacity of MXene devices. In this study, controlled oxidation is employed to create nanoscale holes within MXene, transforming them into holey MXene (H‐MXene) nanosheets. These porous structures shorten ion transport distances and increase ion transport pathways, thereby significantly enhancing the electrochemical storage capacity of MXenes. The resulting H‐MXene micro‐supercapacitors (MSCs) demonstrate exceptional performance, achieving an aerial capacitance 2.5 times that of unmodified MXene electrodes, along with excellent cycling stability, retaining 91.7% of their capacitance after 10 000 cycles. Additionally, a flexible integrated system combining energy storage and sensing functionalities is developed, showcasing its scalability in self‐powered sensing applications. The incorporation of self‐healing polyurethane (PU) enables the device to retain 90% of its storage capacity after undergoing self‐healing. This study presents a novel approach for developing high‐performance MXene‐based energy storage devices and provides valuable insights into efficient ion transport and storage in 2D materials. [ABSTRACT FROM AUTHOR]

The discovery of metal–organic frameworks (MOFs) with novel structures provides significant opportunities for developing porous solids with new properties and enriching the structural diversity of functional materials for various applications. The rational design of building units with specific geometric conformations is essential to direct the construction of MOFs with unique properties. Herein, we leverage a ligand desymmetrization approach to construct a series of new MOFs. A flexible tetratopic carboxylate ligand with a tetrahedral geometry was designed and assembled with a Zr6 cluster, generating four Zr‐based MOF structures: NU‐2600, NU‐2700, NU‐2800, and NU‐1802, in which the ligand configurations and Zr6 cluster connectivities can be controlled by varying solvents and modulators during synthesis. Except for NU‐1802, these represent entirely new topologies. Notably, NU‐1802 exhibits structural flexibility, with up to a 74 % reduction in the unit cell volume as confirmed by single‐crystal X‐ray diffraction studies. Given their microporous structures, we studied the adsorption behaviors of n‐hexane and 2‐chloroethyl ethyl sulfide to explore the structure–property relationships of these MOFs. Overall, this work highlights ligand desymmetrization as a powerful method to enrich MOF structural diversity and access complex MOFs with non‐default topologies suitable for applications such as toxic gas capture. [ABSTRACT FROM AUTHOR]

From a combination of chiral Mn(salen) struts and the tetratopic ligand tetrakis(4-carboxyphenyl)benzene, a large-pore, noncatenated metal-organic framework (MOF) material, MnSO-MOF, has been synthesized. Following solvent exchange with hydrophobic CHCl3, treatment of MnSO-MOF with aqueous H2O2 allowed for the selective demetalation of Mn(salen) struts at and near the surface of the crystals. The resulting crystals displayed greatly enhanced size-selective catalysis compared to the as-synthesized material. Handling of the mechanically fragile MnSO-MOF crystals was greatly facilitated by activation with supercritical CO2. [ABSTRACT FROM AUTHOR]

A diimide based porous organic polymer (POP) post-synthetically reduced with lithium metal demonstrates a drastic increase in selectivity for carbon dioxide over methane. [ABSTRACT FROM AUTHOR]

The article presents a study which examines the reaction of metal-organic frameworks that are being controlled over catenation. It involves the use of a rational design of the organic building block and the isoreticular metal-organic framework (IRMOF) homologous series. It concludes that the degree of catenation of MOFs can be controlled by using an appropriate design of organic building blocks called robust tetratopic carboxylates.

The article suggests the reliability of Sharpless click chemistry in analyzing and modifying non-catenated metal frameworks. The researchers specifically designed a research to identify the reliability of the approach in showing the structure and applicability of metal frameworks. The click chemistry is said to have the ability to ensure engendering chemical diversity of metal frameworks compared to other chemical strategies.

A Zn-based, mixed-ligand (pillared paddlewheel), metal-organic framework (MOF) has been covalently and quantitatively decorated with free carboxylic acids to demonstrate the utility of covalent post-synthesis modification in the construction of otherwise inaccessible carboxy-functionalized MOFs. [ABSTRACT FROM AUTHOR]

A Zn-based, mixed-ligand (pillared paddlewheel), metal–organic framework (MOF) has been covalently and quantitatively decorated with free carboxylic acids to demonstrate the utility of covalent post-synthesis modification in the construction of otherwise inaccessible carboxy-functionalized MOFs. [ABSTRACT FROM AUTHOR]

The article presents a study where a noncatenated hydroxyl-functionalized metal-organic framework (MOF) material was introduced as method for integrating unsaturated metal ions in hydrogen sorption. The study revealed single network cavities-containing with available alcohol qualities through single-crystal X-ray measurement. Additionally, it imparts that the approach may also be desirable for metals that facilitate chemical catalysis or separations.

The article presents an example of node-based postassembly elaboration of a hydrogen sorbing. Metal-organic framework (MOF) material was synthesized by combining a new nonplanar ligand, 4,4',4'',4'''-benzene-1,2,4,5-tetrayltetrabenzoic acid, with a zinc (II) source under solvothermal conditions. Accordingly, an investigation of the empty cavity reveals that modification can substantially modulate the MOF's internal surface are, pore volume, and ability to sorb molecular hydrogen.

Separation of CO2/CH4 mixtures was studied in carborane-based metal–organic framework materials with and without coordinatively unsaturated metal sites; high selectivities for CO2 over CH4 (∼17) are obtained, especially in the material with open metal sites. [ABSTRACT FROM AUTHOR]

Global reliance on fossil fuel combustion for energy production has contributed to the rising concentration of atmospheric CO2, creating significant global climate challenges. In this regard, direct air capture (DAC) of CO2 from the atmosphere has emerged as one of the most promising strategies to counteract the harmful effects on the environment, and the further development and commercialization of this technology will play a pivotal role in achieving the goal of net‐zero emissions by 2050. Among various DAC adsorbents, metal–organic frameworks (MOFs) show great potential due to their high porosity and ability to reversibly adsorb CO2 at low concentrations. However, the adsorption efficiency and cost‐effectiveness of these materials must be improved to be widely deployed as DAC sorbents. To that end, this perspective provides a critical discussion on several types of benchmark MOFs that have demonstrated high CO2 capture capacities, including an assessment of their stability, CO2 capture mechanism, capture‐release cycling behavior, and scale‐up synthesis. It then concludes by highlighting limitations that must be addressed for these MOFs to go from the research laboratory to implementation in DAC devices on a global scale so they can effectively mitigate climate change. [ABSTRACT FROM AUTHOR]

Although technologically promising, the reduction of carbon dioxide (CO2) to produce carbon monoxide (CO) remains economically challenging owing to the lack of an inexpensive, active, highly selective, and stable catalyst. We show that nanocrystalline cubic molybdenum carbide (a-Mo2C), prepared through a facile and scalable route, offers 100% selectivity for CO2 reduction to CO while maintaining its initial equilibrium conversion at high space velocity after more than 500 hours of exposure to harsh reaction conditions at 600°C. The combination of operando and postreaction characterization of the catalyst revealed that its high activity, selectivity, and stability are attributable to crystallographic phase purity, weak CO-Mo2C interactions, and interstitial oxygen atoms, respectively. Mechanistic studies and density functional theory (DFT) calculations provided evidence that the reaction proceeds through an H2-aided redox mechanism. [ABSTRACT FROM AUTHOR]

The article discusses the study by Omar Yaghi and colleauges which describes a promising method of electrocatalytic carbon recycling. It says that authors of the study have developed a molecule-derived catalytic material for the reduction of carbon dioxide to carbon monoxide. Porphyrin stacking and covalent organic frameworks (COFs)-based catalysts are also mentioned.

Metal–organic frameworks (MOF) are a subclass of porous framework materials that have been used for a wide variety of applications in sensing, catalysis, and remediation. Among these myriad applications is their remarkable ability to capture substances in a variety of environments ranging from benign to extreme. Among the most common and problematic substances found throughout the world's oceans and water supplies is [UO2]2+, a common mobile ion of uranium, which is found both naturally and as a result of anthropogenic activities, leading to problematic environmental contamination. While some MOFs possess high capability for the uptake of [UO2]2+, many more of the thousands of MOFs and their modifications that have been produced over the years have yet to be studied for their ability to uptake [UO2]2+. However, studying the thousands of MOFs and their modifications presents an incredibly difficult task. As such, a way to narrow down the numbers seems imperative. Herein, we evaluate the binding behaviors as well as identify the specific binding sites of [UO2]2+ incorporated into six different Zr MOFs to elucidate specific features that improve [UO2]2+ uptake. In doing so, we also present a method for the determination and verification of these binding sites by Anomalous wide-angle X-ray scattering, X-ray fluorescence, and X-ray absorption spectroscopy. This research not only presents a way for future research into the uptake of [UO2]2+ into MOFs to be conducted but also a means to evaluate MOFs more generally for the uptake of other compounds to be applied for environmental remediation and improvement of ecosystems globally. [ABSTRACT FROM AUTHOR]

Highlights • Metal–organic frameworks have been explored as supports for enzyme immobilization. • MOF immobilization enhances enzyme chemical and thermal stability and reusability. • Hierarchically porous MOFs allow both enzyme encapsulation and substrate diffusion. • Mutlienzyme-MOF composites catalyze cascade reactions. Abstract The global catalyst industry is valued at nearly 20 billion USD and demand continues to rise. Enzymes, biological macromolecules, are highly selective and efficient catalysts; however, their commercial implementation has been hindered due to their poor chemical and thermal stability and low reusability. Numerous strategies have been investigated to stabilize enzymes and improve their processability. Recently, metal–organic frameworks (MOFs) have been investigated as enzyme immobilization supports. Herein, we highlight the immobilization of enzymes in MOF cages and pores for catalysis applications and discuss the future of this enzyme encapsulation strategy. [ABSTRACT FROM AUTHOR]

The article discusses the catalytic activity of metal-organic frameworks (MOFs) with metalloporphyrin struts. It points out that metallopophyrins are ideal catalytic struts in MOFs due to their rigidity and well-studied catalytic behavior. It demonstrates that metalloporphyrins can be incorporated into MOF by the appropriate design of organic building blocks.

The article underscores supercritical processing as a route to high internal surface areas and permanent microporosity in metal-organic framework materials. It states that crystalline metal-organic frameworks (MOFs) have evolved as attractive materials for a wide consideration of possible applications, including chemical separations, chemical fuel storage and release, and size-selective molecular catalysis.

The article reports on the purification of metal-organic framework materials (MOFs). It describes the process of synthesizing MOFs using solvothermal procedures due to the inefficiencies of other methods. The article discusses a method of purifying MOFs which addresses several problems regarding isolation of desired products from solvents.

The article cites a study that determined the synthesis and hydrogen uptake properties of carborane-based metal-organic frameworks (MOFs) to achieve high H2 uptake. Carboranes are icosahedral carbon-containing boron clusters that possess material-favorable properties like rigidity. Zinc (Zn)(II) coordination of the deprotonated form of 1,12-dihydroxycarbonyl1-1,12-dicarba-closo-dodecaborene was used as a starting point for carborane-based MOFs.

The development of reticular chemistry has enabled the construction of a large array of metal–organic frameworks (MOFs) with diverse net topologies and functions. However, dominating this class of materials are those built from discrete/finite secondary building units (SBUs), yet the designed synthesis of frameworks involving infinite rod‐shaped SBUs remain underdeveloped. Here, by virtue of a global linker desymmetrization approach, we successfully targeted a novel Cu‐MOF (Cu‐ASY) incorporating infinite Cu‐carboxylate rod SBUs with its structure determined by micro electron diffraction (MicroED) crystallography. Interestingly, the rod SBU can be simplified as a unique cylindric sphere packing qbe tubule made of [43.62] tiles, which further connect the tritopic linkers to give a newly discovered 3,5‐connected gfc net. Cu‐ASY is a permanent ultramicroporous material featuring 1D channels with highly inert surfaces and shows a preferential adsorption of propane (C3H8) over propene (C3H6). The efficiency of C3H8 selective Cu‐ASY is validated by multicycle breakthrough experiments, giving C3H6 productivity of 2.2 L/kg. Density functional theory (DFT) calculations reveal that C3H8 molecules form multiple C−H⋅⋅⋅π and atypical C−H⋅⋅⋅ H−C van der Waals interactions with the inner nonpolar surfaces. This work therefore highlights the linker desymmetrization as an encouraging and intriguing strategy for achieving unique MOF structures and properties. [ABSTRACT FROM AUTHOR]

The development of reticular chemistry has enabled the construction of a large array of metal–organic frameworks (MOFs) with diverse net topologies and functions. However, dominating this class of materials are those built from discrete/finite secondary building units (SBUs), yet the designed synthesis of frameworks involving infinite rod‐shaped SBUs remain underdeveloped. Here, by virtue of a global linker desymmetrization approach, we successfully targeted a novel Cu‐MOF (Cu‐ASY) incorporating infinite Cu‐carboxylate rod SBUs with its structure determined by micro electron diffraction (MicroED) crystallography. Interestingly, the rod SBU can be simplified as a unique cylindric sphere packing qbe tubule made of [43.62] tiles, which further connect the tritopic linkers to give a newly discovered 3,5‐connected gfc net. Cu‐ASY is a permanent ultramicroporous material featuring 1D channels with highly inert surfaces and shows a preferential adsorption of propane (C3H8) over propene (C3H6). The efficiency of C3H8 selective Cu‐ASY is validated by multicycle breakthrough experiments, giving C3H6 productivity of 2.2 L/kg. Density functional theory (DFT) calculations reveal that C3H8 molecules form multiple C−H⋅⋅⋅π and atypical C−H⋅⋅⋅ H−C van der Waals interactions with the inner nonpolar surfaces. This work therefore highlights the linker desymmetrization as an encouraging and intriguing strategy for achieving unique MOF structures and properties. [ABSTRACT FROM AUTHOR]

Boron trifluoride (BF3) is a highly corrosive gas widely used in industry. Confining BF3 in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF3 corrosion. Herein, we designed and synthesized a Lewis basic single‐crystalline hydrogen‐bond crosslinked organic framework (HCOF‐50) for BF3 storage and its application in catalysis. Specifically, we introduced self‐complementary ortho‐alkoxy‐benzamide hydrogen‐bonding moieties to direct the formation of highly organized hydrogen‐bonded networks, which were subsequently photo‐crosslinked to generate HCOFs. The HCOF‐50 features Lewis basic thioether linkages and electron‐rich pore surfaces for BF3 uptake. As a result, HCOF‐50 shows a record‐high 14.2 mmol/g BF3 uptake capacity. The BF3 uptake in HCOF‐50 is reversible, leading to the slow release of BF3. We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF3 ⋅ Et2O. The elucidation of the structure–property relationship, as provided by the single‐crystal X‐ray structures, combined with the high BF3 uptake capacity and controlled sorption, highlights the molecular understanding of framework‐guest interactions in addressing contemporary challenges. [ABSTRACT FROM AUTHOR]

Boron trifluoride (BF3) is a highly corrosive gas widely used in industry. Confining BF3 in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF3 corrosion. Herein, we designed and synthesized a Lewis basic single‐crystalline hydrogen‐bond crosslinked organic framework (HCOF‐50) for BF3 storage and its application in catalysis. Specifically, we introduced self‐complementary ortho‐alkoxy‐benzamide hydrogen‐bonding moieties to direct the formation of highly organized hydrogen‐bonded networks, which were subsequently photo‐crosslinked to generate HCOFs. The HCOF‐50 features Lewis basic thioether linkages and electron‐rich pore surfaces for BF3 uptake. As a result, HCOF‐50 shows a record‐high 14.2 mmol/g BF3 uptake capacity. The BF3 uptake in HCOF‐50 is reversible, leading to the slow release of BF3. We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF3 ⋅ Et2O. The elucidation of the structure–property relationship, as provided by the single‐crystal X‐ray structures, combined with the high BF3 uptake capacity and controlled sorption, highlights the molecular understanding of framework‐guest interactions in addressing contemporary challenges. [ABSTRACT FROM AUTHOR]

The prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O 2 at 465 K. Furthermore, a moderate methane activation energy barrier (E a  = 54 kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barrier to desorption of ΔG = 57 kJ/mol at 473 K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol. [ABSTRACT FROM AUTHOR]

The pollution of surface and groundwater with heavy metals is a serious global concern, both environmentally, as well as with respect to human health. Overabundance of these elements poses severe health risks for humans, and also for other life forms through bioaccumulation along food chains. Therefore, steps should be taken to reduce the amount of such elements in water to acceptable levels. This review looks at metal–organic frameworks (MOFs) which have been recently developed and studied for potential applications in heavy metal removal from water. We provide an overview of the current capabilities and important properties of MOFs used for this purpose. [ABSTRACT FROM AUTHOR]

The metal–organic framework (MOF), NU-1000, and its metalated counterparts have found proof-of-concept application in heterogeneous catalysis and hydrogen storage among others. A vapor-phase technique, akin to atomic layer deposition (ALD), is used to selectively deposit divalent Cu ions on oxo, hydroxo-bridged hexa-zirconium(IV) nodes capped with terminal –OH and –OH2 ligands. The subsequent reaction with steam yields node-anchored, CuII-oxo, hydroxo clusters. We find that cluster installation via AIM (ALD in MOFs) is accompanied by an expansion of the MOF mesopore (channel) diameter. We investigated the behavior of the cluster-modified material, termed Cu-AIM-NU-1000, to heat treatment up to 325 °C at atmospheric pressure with a low flow of H2 into the reaction cell. The response under these conditions revealed two important results: (1) Above 200 °C, the initially installed few-metal-ion clusters reduce to neutral Cu atoms. The neutral atoms migrate from the nodes and aggregate into Cu nanoparticles. While the size of particles formed in the MOF interior is constrained by the width of mesopores (∼3 nm), the size of those formed on the exterior surface of the MOF can grow as large as ∼8 nm. (2) Reduction and release of Cu atoms from the MOFs nodes is accompanied by the dynamic structural transformation of NU-1000 as it reverts back to its original dimension following the release. These results show that while the MOF framework itself remains intact at 325 °C in an H2 atmosphere, the small, AIM-installed CuII-oxo, hydroxo clusters are stable with respect to reduction and conversion to metallic nanoparticles only up to ∼200 °C. [ABSTRACT FROM AUTHOR]

Review: 79 refs. [ABSTRACT FROM AUTHOR]

As we continue to develop metal–organic frameworks (MOFs) for potential industrial applications, it becomes increasingly imperative to understand their mechanical stability. Notably, amongst flexible MOFs, structure-property relationships regarding their compressibility under pressure remain unclear. In this work, we conducted in situ variable pressure powder X-ray diffraction (PXRD) measurements up to moderate pressures (<1 GPa) using a synchrotron source on two families of flexible MOFs: (i) NU-1400 and NU-1401, and (ii) MIL-88B, MIL-88B-(CH3)2, and MIL-88B-(CH3)4. In this project scope, we found a positive correlation between bulk moduli and degree of flexibility, where increased rigidity (e.g., smaller swelling or breathing amplitude) arising from steric hindrance was deleterious, and observed reversibility in the unit cell compression of these MOFs. This study serves as a primer for the community to begin to untangle the factors that engender flexible frameworks with mechanical resilience. all: Understanding the mechanical properties of metal–organic frameworks (MOFs) is crucial for their industrial application, but the compressibility of structurally dynamic MOFs under pressure remains unclear. Here, in situ variable pressure powder X-ray diffraction experiments on two families of dynamic MOFs find that increased structural flexibility results in enhanced mechanical resilience. [ABSTRACT FROM AUTHOR]

Benefiting from inherent lightweight, flexibility, and good adaptability to human body, functional textiles are attracting tremendous attention to cope with wearable issues in sustainable applications around human beings. In this feature article, a comprehensive and thoughtful review is proposed regarding research activities of functional textiles with smart properties. Specifically, a brief exposition of highlighting the significance and rising demands of novel textiles throughout the human society is begun. Next, a systematic review is provided about the fabrication of functional textiles from 1D spinning, 2D modification, and 3D construction, their diverse functionality as well as sustainable applications, showing a clear picture of evolved textiles to the readers. How to engineer the compositions, structures, and properties of functional textiles is elaborated to achieve different smart properties. All these tunable, upgraded, and versatile properties make the developed textiles well suited for extensive applications ranging from environmental monitoring or freshwater access to personal protection and wearable power supply. Finally, a simple summary and critical analysis is drawn, with emphasis on the insight into remaining challenges and future directions. With worldwide efforts, advance and breakthrough in textile functionalization expounded in this review will promote the revolution of smart textiles for intelligence era. [ABSTRACT FROM AUTHOR]

The design and subsequent construction of complex structures using simple building blocks represent an interesting challenge in the field of chemistry. In this paper we describe complex nets of the mtn family and their relationship to the most common binary structure in chemistry, MgCu2. In this bottom-up approach we start by linking simple shapes in space and show the inevitable evolution to highly complex, low density structures. [ABSTRACT FROM AUTHOR]

Often key to boosting photovoltages in photoelectrochemical and related solar-energy-conversion devices is the preferential slowing of rates of charge recombination, especially recombination at semiconductor/solution, semiconductor/polymer, or semiconductor/perovskite interfaces. In devices featuring TiO2 as the semiconducting component, a common approach to slowing recombination is to install an ultrathin metal oxide barrier layer or trap-passivating layer atop the semiconductor, with the needed layer often being formed via atomic layer deposition (ALD). A particularly promising barrier layer material is Nb2O5. Its conduction-band-edge potential ECB is low enough that charge injection from an adsorbed molecular, polymeric, or solid-state light absorber and into the semiconductor can still occur, but high enough that charge recombination is inhibited. While a few measurements of ECB have been reported for conventionally synthesized, bulk Nb2O5, none have been described for ALD-fabricated versions. Here, we specifically determine the conduction-band-edge energy of ALD-fabricated Nb2O5 relative to that of TiO2. We find that, while the value for ALD-Nb2O5 is indeed higher than that for TiO2, the difference is less than anticipated based on measurements of conventionally synthesized Nb2O5 and is dependent on the thermal history of the material. The implications of the findings for optimization of competing interfacial rate processes, and therefore photovoltages, are briefly discussed. [ABSTRACT FROM AUTHOR]

The interactions between uranium and non‐innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium‐based metal–organic frameworks (MOFs) offer a new angle to study these interactions, as these self‐assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non‐innocent linkers. We report the synthesis of the MOF NU‐1700, assembled from U4+‐paddlewheel nodes and catecholate‐based linkers. We propose this highly unusual structure, which contains two U4+ ions in a paddlewheel built from four linkers—a first among uranium materials—as a result of extensive characterization via powder X‐ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations. [ABSTRACT FROM AUTHOR]