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 -NH2-hooked pyridyl linker and tricarboxylate ligand that embraces negatively charged [Cd3(µ2-OH)(COO)6] node and shows pore-space-partitioning by nitrogen-rich flanked organic struts. Owing to the presence of a self-calibrating triazolylamine moiety-grafted auxiliary linker, this anionic MOF delineates reversible and multicyclic fluoro-swapping between protonated-encrypted and deprotonated-decrypted domains in the alternative presence of acid and base. Such pH-triggered, site-specific luminescence variation is utilized to construct highly regenerative anticounterfeiting labels for vivid acronym encryption. The intense fluorescence signature of the material is further harnessed in extremely selective and quick responsive sensing of harmful feed additive roxarsone (ROX) and dichloran (DCNA) pesticide in highly recyclable fashion with significant quenching and nanomolar limits of detection (ROX: 52 ppb; DCNA: 26.8 ppb). Notably, the ultrasensitive fluoro-detection of both these organo-toxins is successfully demonstrated via a handy paper-strip method as well as on the vegetable surface for real-time monitoring. Comprehensive density functional theory studies validate the electron transfer mechanism through redistribution of molecular orbital energy levels by each of the targeted analytes in this electron-rich framework besides evidencing MOF-analyte supramolecular interactions.

Prediction of the capture and utilization of atmospheric acidic gases by azo-based square-pillared fluorinated MOFs.

More than the permissible limit of acidic gases like CO2, SO2, and NO2 in the atmosphere are responsible for the formation of acid rain, the greenhouse effect and many other undesirable environmental hazards. So, the capture and utilization of these gases are essential for mankind. Herein, we proposed an azo-based square pillared MOF, [Ni(MF5)(1,2-bis(4-pyridy)diazene)2]n, with the CUS metal site, i.e. M = Al/Fe, for the selective capture and conversion of acidic gas molecules into commodity chemicals such as cyclic carbonate, sulphite and nitrite. With the aid of Density Functional Theory (DFT), [Ni(MF5)(1,2-bis(4-pyridy)diazene)2]n has been optimized, and the specific force field is derived via guest-host interaction. The Grand Canonical Monte Carlo (GCMC) simulation has been used to explore the guest-host interactions over a wide range of pressures, and their respective stability under pre-humidification is evaluated. The adsorption prediction reveals that MFFIVE-Ni-apy have a higher adsorptive capacity (37.1 mmol g-1), and especially ALFFIVE-Ni-apy possesses a higher affinity towards guest molecules (CO2, SO2) rather than FEFFIVE-Ni-apy. Additionally, the adsorption of gases in the presence of humidity reveals that ALFFIVE-Ni-apy has an optimal adsorption capacity for all investigated acidic gases even at 38.5 RH%. The absorbed acidic gases on MFFIVE-Ni-apy were used for the theoretical investigations on cycloaddition with the aid of DFT as an application perspective of the toxic gases instead of expelling into atmosphere. The Climbing Image Nudged Elastic Band (CI-NEB) approach was used to discover the transition state in this scenario, in which the cycloaddition of adsorbed CO2, SO2, and NO2 gases with epoxides leads to the formation of cyclic carbonates, sulphites, and nitrates, respectively.

Coordination Unsaturation and Basic Site-Immobilized Nanochannel in a Chemorobust MOF for 3-Fold-Increased High-Temperature Selectivity and Fixation of CO2 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 CO2 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 CO2 adsorption at elevated temperatures with considerable MOF-gas interaction. Interestingly, CO2 selectivity unveils nearly a 3-fold improvement upon the rise of temperature, affording a CO2/N2 value of 820 at 313 K, which outperforms many porous adsorbents. Additionally, breakthrough simulation establishes complete separation and attests the potential of this MOF in the separation of flue gas mixture. Importantly, minor CO2 loss during multiple capture-release cycles and under a relative humidity of 75% promise practical usability of the material. Density functional theory (DFT) not only portrays the atomistic level snapshots of temperature-triggered CO2 inclusion inside this microporous vessel alongside the role of diverse CO2-philic sites but also validates the basis of N2-phobicity of an azo-functionalized linker on such increased selectivity. The guest-free MOF further demonstrates non-redox and recyclable CO2 fixation with wide epoxide tolerance under solvent-free mild conditions and even works at atmospheric pressure and room temperature. The crucial roles of high-density acid-base sites in both adsorption and catalysis are supported by control experiments and by comparing the activity of an unfunctionalized MOF. The hydrolytic stability and strong luminescence signature benefit the framework in aqueous-phase selective and fast responsive detection of detrimental roxarsone (ROX) with high quenching (7.56 × 104 M-1) and very low sensitivity (68 nM). Apart from varying degrees of an energy-transfer mechanism, the fluorosensing of ROX is comprehensively supported by in-depth DFT studies that manifest alteration of MOF energy levels in the presence of organoarsenic compounds and depict MOF-analyte supramolecular interactions.

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 [Co2(µ2-OH)(COO)4(H2O)3] secondary building units and neutral [CoN2(COO)2] 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). Alongside remarkable quenching, their nanomolar detection limits (4-AP: 99.5 nM; TNP: 67.2 nM) rank among the lowest reported values in water and corroborate their ultra-sensitivity. Density functional theory (DFT) calculations verify the electron-transfer route of sensing through portraying redistribution of energy levels of molecular orbitals in a three-dimensional network by each analyte and further envisages non-covalent host-guest interactions. Benefiting from the concurrent existence of an open-metal site and a triphenylamine-moiety-functionalized ligand, the activated framework acts as an outstandingly cooperative heterogeneous catalyst in deacetalization-Knoevenagel condensation under mild conditions. The acid-base dual catalysis is detailed for the first time from combined inputs of control experiments and DFT validations. To the best of tandem reaction, larger-sized substrate exhibits insignificant conversion, and certifies rarest pore-fitting induced size-selectivity.

Fluorinated metal organic frameworks, MFFIVE-Ni-L (M = Fe/Al, L = pyr), with coordinatively unsaturated metal site for CO2 separation from flue gas in the presence of humidity by computational methods.

The anthropogenic emission of greenhouse gases, mainly CO2, is considered to be one of the most challenging environmental threats related to global climatic change. Herein, for the first time, we accurately interpreted the interaction of guest molecules such as H2O, CO2 and N2, the main constituent of flue gas, to a coordinatively unsaturated (CUS) square pillared fluorinated metal organic framework (MOF) using a grand canonical Monte Carlo (GCMC) simulation with the help of a specific forcefield. This specific forcefield is derived from the interaction energy profile of the guest molecules to the framework attained from the periodic-density functional theory (DFT) calculations. The DFT-derived forcefield effectively safeguarded the ability of the coordinatively unsaturated square pillared fluorinated MOF for CO2 separation in the presence of moisture.

Water-Tolerant DUT-Series Metal-Organic Frameworks: A Theoretical-Experimental Study for the Chemical Fixation of CO2 and Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ-Valerolactone.

A series of highly thermally and hydrolytically stable porous solids with intriguing properties of zirconium- and hafnium-based metal-organic frameworks (MOFs) [Dresden University of Technology (DUT) series] was synthesized. The DUT MOFs were found to be effective catalysts for both epoxide-CO2 cycloaddition reactions and the catalytic transfer hydrogenation (CTH) of ethyl levulinate (EL). In particular, 12-connected DUT-52(Zr) showed higher catalytic activity than eight- and six-connected catalysts in the synthesis of cyclic carbonates as well as in the production of γ-valerolactone (GVL). The secondary building unit connectivity, coexistence of a moderate number of acidic and basic sites, Brunauer-Emmett-Teller surface area, and combined effects of the pores of the MOFs seem to influence the catalytic activity. The reaction mechanism for the DUT-52(Zr)-mediated cycloaddition reaction of CO2 and the CTH reactions were investigated in detail by using periodic density functional theory calculations. To the best of our knowledge, this is the first detailed computational study for the formation of GVL from EL by using MOF as the catalyst. In addition, grand canonical Monte Carlo simulations predicted the strong interaction of CO2 molecules with the DUT-52(Zr) framework. Remarkably, the DUT-series catalysts possess extraordinary tolerance toward water. Further, DUT-52(Zr) is recyclable and is an efficient catalyst for cycloaddition and CTH reactions for at least five uses without obvious reductions in the activity or structural integrity.