Open-Metal and Carboxamide-Tethered Redox-Active Undulated Framework for Mild-Condition Synthesis of Therapeutic Drugs and Tandem Catalysis with Size-Selectivity.

A mixed-ligand-based thermo-chemically robust and undulated metal-organic framework (MOF) is developed that embraces carboxamide moiety-grafted porous channels and activation-induced generation of open-metal site (OMS). The guest-free MOF acts as an outstanding heterogeneous catalyst in Hantzsch condensation for electronically assorted substrates with low catalyst loading and short duration under greener conditions than the reported materials. Besides Lewis acidic OMS, the carboxamide group activates the substrate via two-point hydrogen bonding, highlighting the effectiveness of custom-made functionalities in this multi-component reaction.

Nitrogen-Rich Covalent Organic Polymer for Metal-Free Tandem Catalysis and Postmetalation-Actuated High-Performance Water Oxidation.

Development of high-performing catalytic materials for selective and mild chemical transformations through adhering to the principles of sustainability remains a central focus in modern chemistry. Herein, we report the template-free assembly of a thermochemically robust covalent organic polymer (COP: ) from 2,2'-bipyridine-5,5'-dicarbonyl dichloride and 2,4,6-tris(4-aminophenyl)triazine as [2 + 3] structural motifs. The two-dimensional (2D) layered architecture contains carboxamide functionality, delocalized π-cloud, and free pyridyl-N site-decked pores.

Heterobimetallic Synergism in Triple-Redox 2D Framework for Largely Boosted Water Oxidation and Flanked Carboxylic-Acid-Triggered Unconventional Tandem Catalysis.

A fish-bone-shaped and thermochemically stable 2D metal-organic framework (MOF) with multimodal active center-decked pore-wall is devised. Redox-active [Co(COO)] node and thiazolo[5,4-d]thiazole functionalization benefit this mixed-ligand MOF exhibiting electrochemical water oxidation with 375 mV overpotential at 10 mA cm current density and 78 mV per dec Tafel slope in alkaline medium. Pair of oppositely oriented carboxylic acids aids postmetalation with transition metal ions to engineer heterobimetallic materials.

Site-Memory-Triggered Reversible Acronym Encryption in a Nitrogen-Rich Pore-Partitioned MOF for Ultrasensitive Monitoring of Roxarsone and Dichloran over Multiple Platform.

Stimuli-responsive emission color modulation in fluorescent metal-organic frameworks (MOFs) promises luminescence-ink-based security application, while task-specific functionality-engineered pores can aid fast-responsive, discriminative, and ultralow detection of harmful organo-aromatics in the aqueous phase. Considering practical applicability, a self-calibrated fluoro-switch between encrypted and decrypted states is best suited for antiforgery measures, whereas image-based monitoring of organo-toxins by repetitive and handy methods over multiple platforms endorses in-field sensory potential. Herein, we constructed a mixed-ligand based chemically stable and bilayered-pillar MOF from -NH-hooked pyridyl linker and tricarboxylate ligand that embraces negatively charged [Cd(μ-OH)(COO)] node and shows pore-space-partitioning by nitrogen-rich flanked organic struts.

Coordination Unsaturation and Basic Site-Immobilized Nanochannel in a Chemorobust MOF for 3-Fold-Increased High-Temperature Selectivity and Fixation of CO under Mild Conditions with Nanomolar Recognition of Roxarsone.

A multifaceted metal-organic framework (MOF) with task-specific site-engineered pores can promise high-temperature and moisture-tolerant capture and non-redox fixation of CO under mild conditions as well as ultrasensitive detection of carcinogenic contaminants in water. Herein, we report a pillar-bilayered MOF that holds a nanochannel with contrasting functionalities for both these sustainable applications with improved performance characteristics. The twofold entangled robust framework exhibits CO adsorption at elevated temperatures with considerable MOF-gas interaction.

Carboxamide functionality grafted entangled Co(II) framework as a unique hydrogen-bond-donor catalyst in solvent-free tandem deacetalization-Knoevenagel condensation with pore-fitting-mediated size-selectivity.

Concerning environmentally benign catalysis with reduced chemical usage, less energy consumption, and waste minimization, metal-organic frameworks (MOFs) with spatially isolated task-specific functionalities not only execute atom-economic important reactions but also enable size-exclusive catalysis at the interface of structure-function synergy. Herein, we synthesized a bipillar-layer Co(II) MOF from the dicarboxylate ligand and carboxamide moiety grafted pyridyl linker. The framework contains a [Co(COO)N] secondary building unit (SBU) and shows excellent hydrolytic stability due to ample non-covalent interactions among the highly conjugated aromatic struts.

Redox-Active and Urea-Engineered-Entangled MOFs for High-Efficiency Water Oxidation and Elevated Temperature Advanced CO Separation Cum Organic-Site-Driven Mild-Condition Cycloaddition.

Development of the multifaceted metal-organic framework (MOF) with in situ engineered task-specific sites can promise proficient oxygen evolution reaction (OER) and high-temperature adsorption cum mild-condition fixation of CO. In fact, effective assimilation of these attributes onto a single material with advance performance characteristics is practically imperative in view of renewable energy application and carbon-footprint reduction. Herein, we developed a three-fold interpenetrated robust Co(II) framework that embraces both redox-active and hydrogen-bond donor moieties inside the microporous channel.

Dangling carboxylic-acid functionality in a fish-bone-shaped 2D framework as a hydrogen-bond-donating catalyst in Friedel-Crafts alkylation.

A two-dimensional, layer-stacked metal-organic framework (MOF) with a dangling acid functionality was developed as the first-ever example of carboxylic-acid-catalysed Friedel-Crafts alkylation with high reusability. Contrary to conventional hydrogen-bond-donating catalysis, a pair of oppositely oriented -COOH moieties acted as potential hydrogen-bonding sites, and efficiently worked for electronically assorted substrates. Control experiments including juxtaposing the performances of a post-metalated MOF and an unfunctionalized analogue explicitly authenticated the carboxylic-acid-mediated catalytic route.

Largely Entangled Diamondoid Framework with High-Density Urea and Divergent Metal Nodes for Selective Scavenging of CO and Molecular Dimension-Mediated Size-Exclusive H-Bond Donor Catalysis.

Pore environment modulation with high-density polarizing groups in metal-organic frameworks (MOFs) can effectively accomplish selective and multicyclic carbon dioxide (CO) adsorption, whereas the incorporation of task-specific organic sites inside these porous vessels promise to evade self-quenching, solubility, and recyclability issues in hydrogen-bond donating (HBD) catalysis. However, concurrent amalgamation of both these attributes over a single platform is rare but extremely demanding in view of sustainable applications. We designed a robust diamondoid framework (CSMCRI = Central Salt and Marine Chemicals Research Institute) from the mixed-ligand assembly of azo group-containing dicarboxylate ligand, urea-functionalized pyridyl linker, and Zn(II) nodes with specific divergent coordination.

Selective and Multicyclic CO Adsorption with Visible Light-Driven Photodegradation of Organic Dyes in a Robust Metal-Organic Framework Embracing Heteroatom-Affixed Pores.

Pore environment modulation with polarizing groups is one of the essential prerequisites for selective carbon dioxide (CO) adsorption in metal-organic frameworks (MOFs), wherein judicious installation of the photocatalytic feature can promise visible light-triggered degradation of toxic organic dye molecules. However, astute amalgamation of both these attributes over a single MOF is rather rare, yet much anticipated in view of sustainable applications. Pore engineering is effectively harnessed in a Zn(II)-based three-dimensional (3D) MOF, (CSMCRI = Central Salt and Marine Chemicals Research Institute), through mixed-ligand assembly of a N-rich linker (), 4,4'-oxybis(benzoic acid) (Hoba) ligand, and [Zn(CO)N] paddle-wheel secondary building units (SBUs).

Brønsted Acid-Functionalized Ionic Co(II) Framework: A Tailored Vessel for Electrocatalytic Oxygen Evolution and Size-Exclusive Optical Speciation of Biothiols.

Metal-organic frameworks (MOFs) not only combine globally demanded renewable energy generation and environmental remediation onto a single platform but also rationalize structure-performance synergies to devise smarter materials with remarkable performance. The robust and non-interpenetrated cationic MOF exemplifies a unique bifunctional scaffold for the efficient electrochemical oxygen evolution reaction (OER) and ultrasensitive monitoring of biohazards. The microporous framework containing Brønsted acid-functionalized [Co(μ-OH)(CO)] secondary building units (SBUs) exhibits remarkable OER performance in 1 M KOH, requiring 410 mV overpotential to obtain 10 mA cm anodic current density, and a low Tafel slope of 55 mV/dec with 93.

Intrinsic-Unsaturation-Enriched Biporous and Chemorobust Cu(II) Framework for Efficient Catalytic CO Fixation and Pore-Fitting Actuated Size-Exclusive Hantzsch Condensation with Mechanistic Validation.

Carbon dioxide (CO) utilization and one-pot Hantzsch condensation denote two important protocols pertinent to sustainable agenda because of the obvious advantages like reduction in chemical usage, short reaction time, and minimum waste generation. To this end, the astute combination of optimum-sized pore structure with built-in Lewis acid center in metal-organic frameworks (MOFs) can bring about such reactions under energetically favorable conditions and offer a step forward to size-exclusive catalysis. The chemoresistant and twofold interpenetrated Cu(II) framework (CSMCRI = Central Salt & Marine Chemicals Research Institute) is built from a -symmetric tricarboxylate ligand and an ,'-donor linker that undergo incisive amalgamation of the paddle-wheel [Cu(COO)] secondary building unit (SBU) and the intrinsically unsaturated Cu(II) node with four coordination.

High-Performance Water Harvester Framework for Triphasic and Synchronous Detection of Assorted Organotoxins with Site-Memory-Reliant Security Encryption via pH-Triggered Fluoroswitching.

Atmospheric water harvesting, triphasic detection of water contaminants, and advanced antiforgery measures are among important global agendas, where metal-organic frameworks (MOFs), as an incipient class of multifaceted materials, can affect substantial development of individual properties at the interface of tailor-made fabrication. The chemically robust and microporous MOF, encompassing contrasting pore functionalization, exhibits an S-shaped water adsorption curve at 300 K with a steep pore-filling step near / = 0.5 and shows reversible uptake-release performance.

Chemically Robust and Bifunctional Co(II)-Framework for Trace Detection of Assorted Organo-toxins and Highly Cooperative Deacetalization-Knoevenagel Condensation with Pore-Fitting-Induced Size-Selectivity.

Acute detection of assorted classes of organo-toxins in a practical environment is an important sustainable agenda, whereas cooperative and recyclable catalysis can mitigate hazards by minimizing energy requirements and reducing waste generation. We constructed an acid-/base-stable Co(II)-framework with a unique network topology, wherein unidirectional porous channels are decorated by anionic [Co(μ-OH)(COO)(HO)] secondary building units and neutral [CoN(COO)] nodes. An intense luminescent signature of the hydrolytically robust framework is harnessed for the selective, fast-responsive, and regenerable detection of two detrimental organo-aromatics, 4-aminophenol (4-AP) and 2,4,6-trinitrophenol (TNP).

Devising Mixed-Ligand Based Robust Cd(II)-Framework From Bi-Functional Ligand for Fast Responsive Luminescent Detection of Fe and Cr(VI) Oxo-Anions in Water With High Selectivity and Recyclability.

Environmental issue related applications have globally surfaced as hottest areas of research, wherein luminescent metal-organic frameworks (LMOFs) with functionalized pores put unique signature in real-time monitoring of multiple classes of toxic compounds, and overcome many of the challenges of conventional materials. We report a two-fold interpenetrated, mixed-ligand Cd(II)-organic framework () [Cd()()(NO)]·DMF·2HO (CSMCRI = Central Salt and Marine Chemical Research Institute, H = 4- (1H-imidazol-1-yl)benzoic acid, = 4,4'-bipyridine) that exemplifies bipillar-layer structure with two different Cd(II) nodes, and displays notable robustness in diverse organic solvents and water. Intense luminescence signature of the activated MOF () is harnessed in extremely selective and fast responsive sensing of Fe ions in aqueous phase with notable quenching constant (1.

Stimuli -triggered fluoro-switching in metal-organic frameworks: applications and outlook.

The design and synthesis of efficient sensor materials with fast-responsive and ultrasensitive detection ability is critical to monitor ecological safety, supervise human health, control industrial wastes, and govern food quality among others. Metal-organic frameworks (MOFs) or coordination polymers (CPs) are a new class of porous crystalline materials that have emerged in several potential applications in last two decades. In particular, applications of MOFs as sensory scaffolds for the detection of hazardous pollutants have attracted researchers due to their fabulous structural characteristics and wide range of pore environment tunability.

Structural Dynamism-Actuated Reversible CO Adsorption Switch and Postmetalation-Induced Visible Light C-H Photocyanation with Rare Size Selectivity in N-Functionalized 3D Covalent Organic Framework.

The impact of dimensionality and flexibility on anticipated properties has prompted major research focus to three-dimensional covalent organic frameworks (3D COFs), where astute functionalization of porous channels for dynamic CO adsorption as well as size-exclusive C-H activation under eco-friendly condition are the most intriguing advanced applications. Herein, we report an imine-based, diamondoid COF that embraces one-dimensional porous channels in spite of ninefold interpenetration. A combination of intrinsic microporosity and pore wall decoration with accessible N atoms from linear strut renders this 3D COF display reasonable CO affinity with decent selectivity (CO/N: 64.

Pore-Functionalized and Hydrolytically Robust Cd(II)-Metal-Organic Framework for Highly Selective, Multicyclic CO Adsorption and Fast-Responsive Luminescent Monitoring of Fe(III) and Cr(VI) Ions with Notable Sensitivity and Reusability.

Metal-organic frameworks (MOFs) show a distinctive pre-eminence over other heterogeneous systems for adsorption of carbon dioxide (CO) gas and fluorescence detection of water contaminating ions, where integration of both these attributes along with enhancement of pore functionality and water stability is crucial for potential applications related to environmental remediation. Pore functionalization has been achieved in a 2-fold interpenetrated, mixed-ligand Cd(II)-framework [Cd()()(NO)]·2DMF·2HO () (H = 4-(4-carboxyphenyl)-1,2,4-triazole, = 4,4'-bipyridine, DMF = dimethylformamide, CSMCRI = Central Salt & Marine Chemicals Research Institute) by utilizing a bifunctional ligand H. The -pillared framework, containing diverse Cd(II) nodes, optimum sized voids, and free N-atom affixed one-dimensional porous channels, shows notable structural robustness in diverse organic solvents and water.

Devising Chemically Robust and Cationic Ni(II)-MOF with Nitrogen-Rich Micropores for Moisture-Tolerant CO Capture: Highly Regenerative and Ultrafast Colorimetric Sensor for TNP and Multiple Oxo-Anions in Water with Theoretical Revelation.

Metal-organic frameworks (MOFs) show distinctive superiority for carbon dioxide (CO) capture and luminescent sensing of toxic pollutants over other materials, where combination of both of these properties together with improvement of hydrolytic stability and pore functionality is critical to environmental remediation applications. The Ni(II) framework [Ni(μ-OH)()()](NO)·6DMA·6MeOH () ( = 4,4',4″-(1-imidazole-2,4,5-triyl)tripyridine, H = azobenzene-4,4'-dicarboxylic acid, DMA = dimethylacetamide, CSMCRI = Central Salt & Marine Chemicals Research Institute), encompassing cationic [Ni(μ-OH)(CO)] SBUs, is solvothermally synthesized from nitrogen-rich and highly fluorescent organic struts. The noninterpenetrated structure, containing free nitrogen atom affixed microporous channels, is stable in diverse organic solvents and weakly basic and acidic aqueous solutions.

Highly Active Ultrasmall Ni Nanoparticle Embedded Inside a Robust Metal-Organic Framework: Remarkably Improved Adsorption, Selectivity, and Solvent-Free Efficient Fixation of CO.

We report integrating additional functionality in an amine decorated, robust metal-organic framework (MOF) by encapsulating Ni nanoparticles (NPs). In-depth characterization of the postmodified structure confirms well-dispersed and ultrasmall NPs inside the framework pores. Although, the surface area is more reduced than pristine MOF, the CO uptake capacity is remarkably increased by 35% with a large 10 kJ/mol rise in adsorption enthalpy that validates favorable interactions between CO and NPs.

Guest-Induced Ultrasensitive Detection of Multiple Toxic Organics and Fe Ions in a Strategically Designed and Regenerative Smart Fluorescent Metal-Organic Framework.

Luminescent metal-organic frameworks (LMOFs) are promising functional materials for sustainable applications, where an analyte-induced multiresponsive system with good recyclability is beneficial for detecting numerous lethal pollutants. We designed and built the dual-functionalized, three-dimensional Zn(II)-framework [Zn( bpg)( azdc)]·(DMF)·(HO) (CSMCRI-1) using an -OH group-integrated bpg linker and a -N═N- moiety containing H azdc ligand, which functions as a unique tetrasensoric fluorescent probe. The activated CSMCRI-1 (1') represents the hitherto unreported pillar-layer framework for extremely selective fluorescence quenching by nitrofurazone antibiotics as well as explosive nitro-aromatic 2,4,6-trinitrophenol, where ultrasensitive detection is achieved for both the electron-lacking analytes.

Unprecedented NH-MIL-101(Al)/n-BuNBr system as solvent-free heterogeneous catalyst for efficient synthesis of cyclic carbonates via CO cycloaddition.

Amine-functionalised framework NH-MIL-101(Al) was synthesized using a solvothermal and microwave method and characterized by PXRD, FT-IR, TGA, SEM-EDX, and BET surface area analysis. The desolvated framework, in the presence of co-catalyst tetrabutylammonium bromide (TBAB), acted as an excellent heterogeneous catalyst for the solvent-free cycloaddition of carbon dioxide (CO) with epoxides, affording five-membered cyclic carbonates. Using styrene oxide, the NH-MIL-101(Al)/TBAB system showed more than 99% conversion, affording 96% yield and 99% selectivity with a turn over frequency of 23.

A Partially Fluorinated, Water-Stable Cu(II)-MOF Derived via Transmetalation: Significant Gas Adsorption with High CO2 Selectivity and Catalysis of Biginelli Reactions.

A partially fluorinated, angular tetracarboxylic acid linker (H4L) incorporating a pendant amine moiety forms a three-dimensional Zn(II) framework, 1. The structure consists of paddle-wheel Zn2(CO2)4 secondary building units (SBUs) and Zn12(CO2)24 supramolecular building blocks (SBBs). Thermal stability of 1 is found to be low.

A Versatile Cu Metal-Organic Framework Exhibiting High Gas Storage Capacity with Selectivity for CO : Conversion of CO to Cyclic Carbonate and Other Catalytic Abilities.

A linear tetracarboxylic acid ligand, H L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) L (M=Zn , Cu ). Framework L can also be obtained from L by post- synthetic metathesis without losing crystallinity. Compared with L , the L framework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, L '.

Significant Gas Adsorption and Catalytic Performance by a Robust Cu(II) -MOF Derived through Single-Crystal to Single-Crystal Transmetalation of a Thermally Less-Stable Zn(II) -MOF.

By using a bent tetracarboxylic acid ligand that incorporates a pendent-NH2 functional group, a 3D Zn(II)-framework (1) based on Zn2 (CO2)4 secondary building units and Zn12 (CO2)24 supramolecular building blocks has been synthesized. Framework 1 is thermally less stable, which precludes its application as a porous framework for gas adsorption or catalytic studies. This framework undergoes single-crystal to single-crystal transmetalation to give isostructural 1Cu.