Heteropolyaromatic Covalent Organic Frameworks via One-Pot Multicomponent Reactions.

Multicomponent reactions (MCRs) offer a platform to create different chemical structures and linkages for highly stable covalent organic frameworks (COFs). As an illustrative example, the multicomponent Povarov reaction generates 2,4-phenylquinoline from aldehydes and amines in the presence of electron-rich alkenes. In this study, we introduce a new domino reaction to generate unprecedented 2,3-phenylquinoline COFs in the presence of epoxystyrene. This work thus presents, for the first time, structural isomeric COFs produced by multicomponent domino and Povarov reactions. Furthermore, 2,3-phenylquinolines can undergo a Scholl reaction to form extended aromatic linkages. With this approach, we synthesize two thermally and chemically stable MCR-COFs and two heteropolyaromatic COFs using both domino and in situ domino and Scholl reactions. The structure and properties of these COFs are compared with the corresponding 2,4-phenylquinoline-linked COF and imine-COF, and their activity toward benzene and cyclohexane sorption and separation is investigated. The position of the pendant phenyl groups within the COF pore plays a crucial role in facilitating the industrially important sorption and separation of benzene over cyclohexane. This study opens a new avenue to construct heteropolyaromatic COFs via MCR reactions.

A Novel Deep Learning-Based Classification Framework for COVID-19 Assisted with Weighted Average Ensemble Modeling.

COVID-19 is an infectious disease caused by the deadly virus SARS-CoV-2 that affects the lung of the patient. Different symptoms, including fever, muscle pain and respiratory syndrome, can be identified in COVID-19-affected patients. The disease needs to be diagnosed in a timely manner, otherwise the lung infection can turn into a severe form and the patient's life may be in danger. In this work, an ensemble deep learning-based technique is proposed for COVID-19 detection that can classify the disease with high accuracy, efficiency, and reliability. A weighted average ensemble (WAE) prediction was performed by combining three CNN models, namely Xception, VGG19 and ResNet50V2, where 97.25% and 94.10% accuracy was achieved for binary and multiclass classification, respectively. To accurately detect the disease, different test methods have been proposed and developed, some of which are even being used in real-time situations. RT-PCR is one of the most successful COVID-19 detection methods, and is being used worldwide with high accuracy and sensitivity. However, complexity and time-consuming manual processes are limitations of this method. To make the detection process automated, researchers across the world have started to use deep learning to detect COVID-19 applied on medical imaging. Although most of the existing systems offer high accuracy, different limitations, including high variance, overfitting and generalization errors, can be found that can degrade the system performance. Some of the reasons behind those limitations are a lack of reliable data resources, missing preprocessing techniques, a lack of proper model selection, etc., which eventually create reliability issues. Reliability is an important factor for any healthcare system. Here, transfer learning with better preprocessing techniques applied on two benchmark datasets makes the work more reliable. The weighted average ensemble technique with hyperparameter tuning ensures better accuracy than using a randomly selected single CNN model.

Integrating Bifunctionality and Chemical Stability in Covalent Organic Frameworks via One-Pot Multicomponent Reactions for Solar-Driven H2O2 Production.

Multicomponent reactions (MCRs) can be used to introduce different functionalities into highly stable covalent organic frameworks (COFs). In this work, the irreversible three-component Doebner reaction is utilized to synthesize four chemically stable quinoline-4-carboxylic acid DMCR-COFs (DMCR-1-3 and DMCR-1NH) equipped with an acid-base bifunctionality. These DMCR-COFs show superior photocatalytic H2O2 evolution (one of the most important industrial oxidants) compared to the imine COF analogue (Imine-1). This is achieved with sacrificial oxidants but also in pure water and under an oxygen or air atmosphere. Furthermore, the DMCR-COFs show high photostability, durability, and recyclability. MCR-COFs thus provide a viable materials' platform for solar to chemical energy conversion.

Efficient and Highly Selective CO2 Capture, Separation, and Chemical Conversion under Ambient Conditions by a Polar-Group-Appended Copper(II) Metal-Organic Framework.

A polar sulfone-appended copper(II) metal-organic framework (MOF; 1) has been synthesized from the dual-ligand approach comprised of tetrakis(4-pyridyloxymethylene)methane and dibenzothiophene-5,5'-dioxide-3,7-dicarboxylic acid under solvothermal conditions. This has been studied by different techniques that included single-crystal X-ray diffractometry, based on which the presence of Lewis acidic open-metal sites as well as polar sulfone groups aligned on the pore walls is identified. MOF 1 displays a high uptake of CO2 over N2 and CH4 with an excellent selectivity (S = 883) for CO2/N2 (15:85) at 298 K under flue gas combustion conditions. Additionally, the presence of Lewis acidic metal centers facilitates an efficient size-selective catalytic performance at ambient conditions for the conversion of CO2 into industrially valuable cyclic carbonates. The experimental investigations for this functional solvent-free heterogeneous catalyst are also found to be in good correlation with the computational studies provided by configurational bias Monte Carlo simulation for both CO2 capture and its conversion.

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications.

Among the recent developments in metal-organic frameworks (MOFs), porous layered coordination polymers (CPs) have garnered attention due to their modular nature and tunable structures. These factors enable a number of properties and applications, including gas and guest sorption, storage and separation of gases and small molecules, catalysis, luminescence, sensing, magnetism, and energy storage and conversion. Among MOFs, two-dimensional (2D) compounds are also known as 2D CPs or 2D MOFs. Since the discovery of graphene in 2004, 2D materials have also been widely studied. Several 2D MOFs are suitable for exfoliation as ultrathin nanosheets similar to graphene and other 2D materials, making these layered structures useful and unique for various technological applications. Furthermore, these layered structures have fascinating topological networks and entanglements. This review provides an overview of different aspects of 2D MOF layered architectures such as topology, interpenetration, structural transformations, properties, and applications.

Design of Fluorescent and Robust Covalent Organic Framework Host Matrices for Illuminating Mechanistic Insight into Solvatochromic Decoding.

Two functional covalent organic frameworks (COFs), constructed from 3-connected triazine-based amine or hydrazine with linear dialdehyde, are decorated with molecular docking sites to showcase their solvatochromic decoding behavior toward volatile solvent molecules (VSMs). These luminescent and crystalline COFs, namely, COF-N and COF-NN, are characterized by numerous analytical techniques. After accommodation of different VSMs as guests, the inclusion compounds of COF-N and COF-NN display solvatochromism. More fascinatingly, the singlet energy, band gaps, and lifetime of these VSM-accommodated COF-N and COF-NN are linearly correlated with the properties of VSMs. Density functional theory (DFT) and Monte Carlo simulation studies further support the interaction of VSMs with COF-N and COF-NN. The presence of an extra amine functionality in COF-NN leads to the better interaction with VSMs and, therefore, results in different modes of interaction and correlation. Considering their inestimable chemical diversity, this study introduces a new path for finely tuned solvatochromic properties by COFs.

Comprehensive Structural and Microscopic Characterization of an Azine-Triazine-Functionalized Highly Crystalline Covalent Organic Framework and Its Selective Detection of Dichloran and 4-Nitroaniline.

In recent years, luminescent covalent organic frameworks (COFs) constructed with nitrogen-rich building units have been the target for selective detection of electron-deficient pollutants to serve for a clean environment. In order to contribute to these imperative applications, an azine-triazine-based COF (ANCOF) has been solvothermally synthesized and structurally characterized by a variety of analytical methods for comprehensive studies. ANCOF possesses micropores with a rare ABAB stacking, high thermal and chemical stabilities, and a Brunauer-Emmett-Teller surface area of 565 m2 g-1. On the other hand, ANCOF exhibits excellent luminescent property in the presence of different solvents marked by the wavelength shift due to polarity. Exploiting the bluish-white emission of ANCOF in aqueous medium, it has been found to be an excellent probe for the discriminative and selective detection of dichloran (DCNA) and 4-nitroaniline (4-NA) with detection limits of 142 and 89 ppb, respectively. A distinguishable color change for DCNA and 4-NA has been reflected by UV illumination, fluorescence microscopy, and a handy paper strip method. Time-resolved fluorescence studies, spectral overlap, density functional theory, and configurational bias Monte Carlo molecular simulation have been utilized to understand the mechanism of action and interaction of DCNA and 4-NA with the host ANCOF. The selectivity of ANCOF toward DCNA and 4-NA in the presence of other analytes and the recyclability after sensing experiments have been successfully demonstrated. Furthermore, the stability of ANCOF has been confirmed by powder X-ray diffraction and field emission scanning electron microscopy with good retention of crystallinity and morphology. To the best of our knowledge, this is the first COF employed for the detection of amine derivatives in aqueous solution combining both experimental and computational studies.

Polar Sulfone-Functionalized Oxygen-Rich Metal-Organic Frameworks for Highly Selective CO2 Capture and Sensitive Detection of Acetylacetone at ppb Level.

A rational combination of an oxygen-rich pyridyl substituted tetrapodal ligand, tetrakis(4-pyridyloxymethylene)methane (TPOM), and a polar sulfone-functionalized conjugated bent dicarboxylate linker, dibenzothiophene-5,5'-dioxide-3,7-dicarboxylic acid (H2(3,7-DBTDC)), with d10 metal centers, Zn(II) and Cd(II), has led to the construction of two new three-dimensional (3D) metal-organic frameworks,{[Zn2(TPOM)(3,7-DBTDC)2]·7H2O·DMA}n (1) and {[Cd2(TPOM)(3,7-DBTDC)2]·6H2O·3DMF}n (2). Single-crystal X-ray analysis indicates that 1 is a 3D framework with a dinuclear repeating unit having two different Zn(II) centers (tetrahedral and square pyramidal) and 2 is a 3D framework comprised of a dinuclear repeating unit with one crystallographically independent distorted pentagonal bipyramidal Cd(II) coordinated to chelating/bridging carboxylates and nitrogen atoms of the TPOM ligand. In both cases, the pores are aligned with oxygen atoms of the TPOM ligand and decorated with polar sulfone moieties. On the basis of the stability established by thermogravimetric analysis and powder X-ray diffraction (PXRD) and the presence of large solvent accessible voids (25.4% for 1 and 40.6% for 2), gas sorption studies of different gases (N2, CO2, and CH4) and water vapor have been explored for both 1 and 2. The CO2 sorption isotherm depicts type I isotherm with an uptake of 93.6 cm3 g-1 (for 1) and 100.6 cm3 g-1 (for 2) at 195 K. Additionally, sorption of CO2 is highly selective over that of N2 and CH4 for both 1 and 2 due to the strong quadrupolar interactions between sulfone moieties and CO2 molecules. Configurational bias Monte Carlo (CBMC) molecular simulation has further justified the highly selective CO2 capture. On the other hand, the luminescence nature of 1 and 2 has been employed for highly selective detection of acetylacetone in aqueous methanol with a limit of 59 ppb in 1 and 66 ppb in 2, which are among the best reported values so far in the literature. The Stern-Volmer plots, spectral overlap, density functional theory calculations, CBMC simulation, and time-resolved lifetime measurements have been utilized for an extensive mechanistic study. The exclusive selectivity for acetylacetone in 1 and 2 have been confirmed by competitive selectivity test. Both exhibited good recyclability and stability after sensing experiments analyzed by fluorescence, PXRD, and field emission scanning electron microscopy studies.

Structural Diversity in Luminescent MOFs Containing a Bent Electron-rich Dicarboxylate Linker and a Flexible Capping Ligand: Selective Detection of 4-Nitroaniline in Water.

A combination of a bent bis(naphthalene) and hydroxy-based dicarboxylate linker and a flexible bis(tridentate)polypyridyl ligand has been employed to self-assemble with two different d10 metal centers, ZnII and CdII , to form structurally diversified luminescent metal-organic frameworks, [Zn2 (tpbn)(mbhna)2 (H2 O)2 ]⋅4 H2 O⋅1.5DMF (1) and {[Cd2 (tpbn)(mbhna)2 ]⋅2DMF}n (2), respectively (where, tpbn=N,N',N'',N'''-tetrakis(pyridine-2-ylmethyl)butane-1,4-diamine and H2 mbhna=4,4'-methylene-bis[3-hydroxy-2-naphthalene carboxylic acid]). Both 1 and 2 are characterized and analyzed by various analytical techniques including single-crystal X-ray diffractometry. Their excellent emissive nature is studied in different solvents and further utilized to selectively detect aromatic amines, particularly 4-nitroaniline in water with detection limits at sub-ppm level. The difference in sensing activity of 1 and 2 toward 4-NA is corroborated well with their structures. The mechanism of action has been established through Stern-Volmer plot, spectral overlap, time-resolved lifetime studies and HOMO-LUMO energy calculations. In addition, 1 and 2 are found to be recyclable and display good stability after sensing experiments.

Strategic Construction of Highly Stable Metal-Organic Frameworks Combining Both Semi-Rigid Tetrapodal and Rigid Ditopic Linkers: Selective and Ultrafast Sensing of 4-Nitroaniline in Water.

In this work, we have designed two new 3D metal-organic frameworks (MOFs), {Zn4(TPOM)(1,4-NDC)4} n (1) and {Ni2(TPOM)(1,4-NDC)2(H2O)2} n (2), utilizing both semi-rigid tetrapodal neutral linker, tetrakis(4-pyridyloxymethylene)methane (TPOM) and rigid ditopic anionic linker, 1,4-naphthalene dicarboxylic acid (H2(1,4-NDC)). On the basis of the single-crystal X-ray diffraction, 1 has a 3D structure with star-shaped pores arising from four-fold symmetry due to the presence of a paddle-wheel core [Zn2(O2CC12H6)4(C6H4N)2] as a subunit, whereas 2 consists of a zig-zag 3D framework with strong hydrogen bonding between the coordinated water molecules and coordinated carboxylate groups. Their thermogravimetric analysis indicates an extraordinary thermal stability: 1 up to 400 °C and 2 up to 350 °C. In addition to elemental microanalysis and spectroscopic characterization (UV-vis and infra-red spectroscopy), the bulk phase purity of 1 and 2 as well as hydrolytic stability of 1 are established by powder X-ray diffraction. Exploiting the luminescence nature of 1, both solvent-dependent fluorescence properties and sensing of various amines in aqueous medium are demonstrated. It exhibits good sensing ability toward 4-nitroaniline (4-NA) and 2,6-dichloro-4-nitroaniline (2,6-DCNA; a broad spectrum pesticide belonging to toxicity class III) with the lowest detection limit of 88 ppb and 0.28 ppm, respectively. The mechanism of action has been established through Stern-Volmer plots, time-resolved fluorescence studies, spectral overlap, and density functional theory calculations. The recyclability and stability of 1 after sensing experiments also reveal no change in its crystallinity. Furthermore, selectivity test and time-dependent detection for 4-NA have been successfully demonstrated. For practical applications, naked eye detection of 4-NA using test paper strips is also displayed.

Design and Development of Fluorescent Sensors with Mixed Aromatic Bicyclic Fused Rings and Pyridyl Groups: Solid Mediated Selective Detection of 2,4,6-Trinitrophenol in Water.

For a strategic incorporation of both π-electron-rich moieties and Lewis basic moieties acting as hydrogen bonding recognition sites in the same molecule, two new fluorescent sensors, N,N'-bis(anthracen-9-ylmethyl)-N,N'-bis(pyridin-2-ylmethyl)butane-1,4-diamine (banthbpbn, 1) and N,N'-bis(naphthalen-1-ylmethyl)-N,N'-bis(pyridin-2-ylmethyl)butane-1,4-diamine (bnaphbpbn, 2), have been developed for the selective detection of highly explosive 2,4,6-trinitrophenol (TNP) in water. Each of the two identical ends of these sensors that are linked with a flexible tetra-methylene spacer contains a mixed aromatic bicyclic fused ring (anthracene or naphthalene) and a pyridyl group. These are synthesized via the simple reduced Schiff base chemistry, followed by the nucleophilic substitution reaction under basic conditions in high yields. Both 1 and 2 were characterized by Fourier transform infrared, UV-vis, and NMR (1H and 13C) spectroscopy, and high-resolution mass spectrometry. The bulk phase purity of 1 and 2 and their stability in water were confirmed by powder X-ray diffraction (PXRD). Utilizing the effect of solvents on their emission spectra as determined by fluorescence spectroscopy, spectral responses for 1 and 2 toward various nitro explosives were recorded to determine a detection limit of 0.6 and 1.6 ppm, respectively, for TNP in water via the "turn-off" quenching response. Also, the detailed mechanistic investigation for their mode of action through spectral overlap, lifetime measurements, Stern-Volmer plots, and density functional theory calculations reveals that resonance energy transfer and photoinduced electron transfer processes, and electrostatic interactions are the key aspects for the turn-off response toward TNP by 1 and 2. In addition, the selectivity for TNP has been found to be more in 1 compared to 2. Both exhibit good recyclability and stability after sensing experiments, which is confirmed by PXRD and field-emission scanning electron microscopy.

Neutral Luminescent Metal-Organic Frameworks: Structural Diversification, Photophysical Properties, and Sensing Applications.

Utilizing flexible bis(tridentate)polypyridyl ligands, the two new luminescent 2D metal organic frameworks {Zn2(tpbn)(2,6-NDC)2}n (1) and {[Zn2(tphn)(2,6-NDC)2]·4H2O}n (2), where tpbn = N,N',N″,N‴-tetrakis(2-pyridylmethyl)-1,4-diaminobutane, tphn = N,N',N″,N‴-tetrakis(2-pyridylmethyl)-1,6-diaminohexane, and 2,6-H2NDC = 2,6-naphthalenedicarboxylic acid, have been isolated in good yields under solvothermal conditions. Their solid-state molecular structures have been determined by single-crystal X-ray diffractometry. Both 1 and 2 have pentacoordinated Zn(II) centers with an N3O2 environment from three nitrogen atoms of the tpbn or tphn ligand and two carboxylate oxygen atoms from two different 2,6-NDC linkers. However, the binding modes of the tridentate part of polypyridyl ligands to the Zn(II) center are different in 1 and 2-meridional (tpbn) vs facial (tphn) due to an increase (1.5 times) in the methylene chain length. Thus, the binding mode of 2,6-NDC to the Zn(II) center differs: bis(monodentate) syn-anti in 1 and bis(monodentate) syn-syn in 2. This difference in binding modes of the components has a profound effect on the conformation of the six-membered ring (metal centers are considered as the vertices in it) within the 2D framework: honeycomb vs chair form for 1 and 2, respectively. In addition to further characterization by elemental analysis and UV-vis and FT-IR spectroscopy, their framework stabilities in water and thermal properties have been studied by powder X-ray diffraction and thermogravimetric analysis, respectively. On the basis of thermodiffractometry, 1 and 2 retain their crystallinity and overall structure up to 350 and 325 °C, respectively. Their luminescent properties have been utilized to demonstrate sensing of various solvents as well as nitro-aromatic compounds in water, which correlate well with their structural differences. Through the spectral overlap, lifetime measurements, and nature of the Stern-Volmer plots, the fluorescence quenching pathway for the nitro-analytes, particularly 2,4,6-trinitrophenol (TNP), is established for 1 and 2. Their recyclability and stability after sensing experiments are found to be excellent.