Two Metal-Organic Frameworks with a Fused Cis-Decalin Conformation for Multimedia Iodine Capture.

The extensive growth of nuclear power plants has a severe detrimental effect on human health and the surroundings due to the uncontrolled and unfiltered release of radioactive wastes into the environment. One such radioactive waste is 129I which has a fatal effect when released into the air or water bodies. Hence, molecular and ionic iodine capture from multimedia has become an important area of interest in the recent past. This work is aimed at introducing two 2D metal-organic frameworks with a fused cis-decalin conformation, {[Zn2(tpbn)(fdc)2]·6H2O}n (1) and {[Cd2(tpbn)(fdc)2(H2O)2]·2H2O}n (2), synthesized at room temperature utilizing a combination of M(OAc)2·2H2O (M: Zn/Cd), a neutral flexible ligand, tpbn, and a simple commercially available furan dicarboxylate, fdc2-, for the target application. The polarizing nature of the furan moieties and the oxygen rich pores in 1 and 2 facilitate the easy capture of molecular iodine from both the vapor phase and aqueous media with high uptake values. Furthermore, their efficiency was tested for the practical application under real-world conditions using river and seawater. In addition to confirming their recyclability with the retention of structural integrity, the interaction between 1 and 2 with iodine has also been established with experimental and theoretical calculations.

One-Pot Synthesis of Vinylogous Cyano Aminoaryls (VinCAs) as Benzenic Fluorophores: Tailoring Diverse Emission Colors for White Light Emitting Materials and Cell Imaging.

Donor-acceptor-based organic small molecules with an electronic push-pull effect can demonstrate intramolecular charge transfer to show interesting photoluminescence properties. This is an essential criterion for designing fluorogenic probes for cell imaging studies and the development of organic light-emitting diodes. Now, to design such optical materials sometimes it is necessary to tune the band gap by controlling the energies of the highest occupied molecular orbital and lowest unoccupied molecular orbital. Typically, the band gaps could be modulated by installing unsaturated handles between electron-rich donors and electron-deficient acceptors. However, these methods are often synthetically and economically challenging due to the involvement of expensive catalysts and difficult reaction setups. In our present study, we show a straightforward, cost-effective method for obtaining a series of donor-acceptor-type Vinylogous Cyano Aminoaryls (VinCAs) with diverse emission colors. Further studies reveal that these VinCAs can serve as effective cell imaging agents, showcasing potential use in chemical biology. Additionally, these molecules could be further used to generate white light emission (WLE), showing their potential utility in advanced lighting technologies.

Strategic Design of Non-d10 Luminescent Metal-Organic Frameworks as Dual-Mode Ultrafast and Selective Sensing Platforms for Aldehydes at the ppb Level.

Utilizing a cautious design of luminescent MOFs of non-d10 divalent transition metals based on two factors (metal nodes in an octahedral geometry to minimize nonradiative energy dissipation and tailored organic chromophores), this work reports {[Ni2(oxdz)2(tpbn)]}n (1), {[Ni2(oxdz)2(tphn)]}n (2), and {[Ni2(oxdz)2(tpon)]}n (3), synthesized at room temperature, varying the spacer length of tpbn/tphn/tpon (four, six, and eight CH2 groups, respectively). This subtle change in 1-3 is correlated to their hydrophobicity and polarizing power via water vapor sorption and selective and sensitive detection of aldehydes at the ppb level, respectively. A decrease in water vapor uptake (14.8, 8.95, and 3.19 mmol g-1 for 1-3, respectively) is observed with an increase in their hydrophobicity. On the other hand, the solution phase detection limits of acetaldehyde and benzaldehyde (2.42 and 6.71 ppb for 1, 2.77 and 4.08 ppb for 2, and 10.35 and 10.4 ppb for 3, respectively) show a similar trend for their polarizing power. The best performance of 1 is expanded to the vapor-phase detection of acetaldehyde (297% luminescence enhancement) under different pH conditions. The second mode of detection of acetaldehyde via the metal-centered electrochemical behavior of 1 provides detection limits of 38.2 and 71.5 ppb at pH 7 and 13, respectively.

A Multivariate 2D Metal-Organic Framework with Open Metal Sites for Catalytic CO2 Cycloaddition and Cyanosilylation Reactions.

This work reports the synthesis of a dual functional 2D framework, {[Zn2(4-tpom)2(oxdz)2]·4H2O}n (1), at room temperature, where a bent dicarboxylate, oxdz2- (4,4'-(1,3,4-oxadiazole-2,5-diyl)dibenzoate), and a neutral flexible N-donor linker, 4-tpom (tetrakis(4-pyridyloxymethylene)methane), are utilized. Its single-crystal X-ray analysis indicated a 2-fold interpenetrated 2D framework having tetracoordinated Zn(II) centers and dangling pyridyl groups. Its further characterization was carried out with elemental microanalysis, FTIR spectroscopy, TG analysis, and powder X-ray diffraction. The tetracoordinated Zn(II) centers as active Lewis acidic sites and the N atoms of 4-tpom as Lewis basic sites in 1 are explored for its functioning as a heterogeneous catalyst in two important reactions, (i) cycloaddition of CO2 with various epoxides and (ii) cyanosilylation reaction under solvent-free conditions. We could successfully show the cycloaddition of styrene oxide with CO2 (99% conversion) under balloon pressure with low catalyst (0.2-0.3 mol %) and cocatalyst (0.5-0.75 mol %) loadings, which is otherwise difficult to achieve. It was observed that all the substrates (aromatic and aliphatic), irrespective of their sizes, showed conversion percentage >99%. In the cyanosilylation reaction, a conversion of 96% was obtained with 1.5 mol % of 1 at room temperature for 12 h. This framework emerged as an excellent recyclable catalyst for both the reactions.

Use of discarded corneo-scleral rims to create cornea-like tissue.

BACKGROUND: Corneal disease is a major cause of blindness. Transplantation of cadaver-derived corneas (keratoplasty) is still the current therapy of choice; however, the global shortage of donor corneas continues to drive a search for alternatives. To this end, biosynthetic corneal substitutes have recently begun to gain importance. Here, we present a novel method for the generation of a cornea-like tissue (CLT), using corneo-scleral rims discarded after keratoplasty. METHODS AND RESULTS: Type I collagen was polymerized within the corneo-scleral rim, which functioned as a 'host' mould, directing the 'guest' collagen to polymerize into disc-shaped cornea-like material (CLM), displaying the shape, curvature, thickness, and transparency of normal cornea. This polymerization of collagen appears to derive from some morphogenetic influence exerted by the corneo-scleral rim. Once the CLM had formed naturally, we used collagen crosslinking to fortify it, and then introduced cells to generate a stratified epithelial layer to create cornea-like tissue (CLT) displaying characteristics of native cornea. Through the excision and reuse of rims, each rim turned out to be useful for the generation of multiple cornea-shaped CLTs. CONCLUSIONS: The approach effectively helps to shorten the gap between demand and supply of CLMs/CLTs for transplantation. We are exploring the surgical transplantation of this CLT into animal eyes, as keratoprostheses, as a precursor to future applications involving human eyes. It is possible to use either the CLM or CLT, for patients with varying corneal blinding diseases.

Strategic design of a rare trigonal symmetric luminescent covalent organic framework by linker modification.

We designed a trigonal symmetric imine-linked covalent organic framework (COF), TFPC-DAB, with control over the angularity of the building units, where a bent C2-symmetric diamine, such as 1,3-diaminobenzene (1,3-DAB or DAB), with an exo-angle of 120° was used instead of those with an exo-angle of 180°, in combination with a C3-symmetric trialdehyde, such as tri(4-formylphenoxy)cyanurate (TFPC). Its synthesis was accomplished by reacting the building units in a mixture of mesitylene/dioxane/6 M acetic acid under solvothermal conditions. The phase purity, thermal stability, and porosity of TFPC-DAB were established by various analytical techniques. Utilizing the Density Functional Tight Binding (DFTB+) simulation and Pawley refinement, the best fit of the small angle x-ray pattern was found to have an AA stacking of TFPC-DAB in the trigonal space group P3 with low refinement parameters. Such smart materials are in huge demand to detect hazardous corrosive chemicals, such as HCl and NH3. The dual features of electron deficient π-acidic triazine moiety and heteroatoms (N/O) from TFPC and electron rich phenyl units from DAB embodied in the framework enhance its luminescent property and thereby make it suitable for solvent-based HCl and NH3 sensing. The detection limits for HCl and NH3 in methanol were found to be 14 and 82 ppb, respectively. The effect of solvent polarity on the sensing studies was observed with much lower detection limits in dioxane: 2.5 and 11 ppb for HCl and NH3, respectively. A detailed theoretical calculation using density functional theory and configurational bias Monte Carlo modules was conducted for understanding interactions between the COF and HCl or NH3 analytes.

Synthesis of modified bile acids via palladium-catalyzed C(sp3)-H (hetero)arylation.

A Pd(II)-catalyzed strategy for the diastereo- and regioselective (hetero)arylation of unactivated C(sp3)-H bonds in bile acids is accomplished with aryl and heteroaryl iodides under solvent-free conditions using the 8-aminoquinoline auxiliary as a directing group. This methodology demonstrated excellent functional group tolerance with respect to aryl/heteroaryl iodides on O-protected N-(quinolin-8-yl)cholyl/deoxycholyl amides to afford ß-C(sp3)-H (hetero)arylated products in good-to-excellent yields. Moreover, the 8-aminoquinoline (AQ) auxiliary can easily be removed to obtain modified bile acids.

A convenient route to a vinylogous dicyano aryl based AIEgen with switchable mechanochromic luminescence properties.

Molecules with solid state luminescence and mechanochromic luminescence properties have attracted immense interest owing to their potential application in the areas of organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), optoelectronic devices, fluorescence switches, mechano-sensors and data storage. Herein we report a convenient two step synthetic protocol to obtain a couple of luminescent molecules. Using these, a comparative study has been performed to showcase the importance of the weak π⋯π interactions to observe the aggregation induced emission (AIE) and solid-state mechanochromic luminescence. The most fascinating part of this report is to observe the switchable fluorescent dark and bright states of the solid AIEgen. We have also demonstrated the use of the AIEgen to detect volatile organic compounds.

Exploiting a Multi-Responsive Oxadiazole Moiety in One Three-Dimensional Metal-Organic Framework for Remedies to Three Environmental Issues.

Multifunctional metal-organic frameworks (MOFs) rely on the properties of metal centers (nodes) and/or linkers (struts) for their diverse applications in the emerging field of research. Currently, there is a huge demand for MOF materials in the field of capture/fixation/sensing of air pollutants, harmful chemical effluents, and nuclear waste. However, it is a challenging task to utilize one MOF for providing remedies to all these issues. On the basis of our current research activities, we have identified that an oxadiazole moiety-a five-membered ring with two different heteroatoms (O and N)-in a carboxylate linker can be the key to generating such MOF materials for its (a) inherent polarizable nature and molecular docking ability and (b) photoluminescence properties. In this work, we report a 3D MOF {[Co2(oxdz)2(tpbn)(H2O)2]·4H2O}n (1), self-assembled at room temperature from a three-component reaction, with an oxadiazole moiety (where H2oxdz = 4,4'-(1,3,4-oxadiazole-2,5-diyl)dibenzoic acid and tpbn = N,N',N,"N″'-tetrakis(2-pyridylmethyl)-1,4-diaminobutane). The inherent polarizable nature of the oxadiazole moiety in 1 has been efficiently exploited for (i) multimedia iodine capture and (ii) fixation of CO2 under solvent-free and ambient conditions. On the other hand, the luminescent nature of the framework is found to be an efficient, highly preferred turn-on sensor for the ultra-fast detection of ketones with a limit as low as parts-per-trillion (mesitylene oxide: 447 ppt; cycloheptanone: 4.7 ppb; cyclohexanone: 17.2 ppb; acetylacetone: 18 ppb).

Two pillared-layer metal-organic frameworks based on the pinwheel trinuclear carboxylate-clusters of Zn(II) and Co(II): synthesis, crystal structures, magnetic study, and Lewis acid catalysis.

Using a dicarboxylic acid, [1,1'-biphenyl]-4,4'-dicarboxylic acid (H2L1) and an exobidentate ligand, (1E,1'E)-N,N'-(1,4-phenylene)bis(1-(pyridin-4-yl)methanimine) (L2), two 3D interpenetrated networks, {[Zn3(L1)3(L2)]·9H2O}n (Zn-MOF) and {[Co3(L1)3(L2)(DMF)]·0.5DMF}n (Co-MOF), have been prepared in good yields. The crystal structure analysis of Zn-MOF and Co-MOF revealed that both have a 3D pillared-layer structure based on pinwheel trinuclear metal-carboxylate clusters as secondary building units (SBUs). Furthermore, the structures also exhibited three-fold interpenetration. Although the overall networks in Zn-MOF and Co-MOF showed significant resemblances, there are marked differences in their crystal structures, which are associated with the coordination environment of the metal centre and the binding modes of the carboxylates. Gas adsorption studies (N2 at 77 K and 1 bar) indicated that Co-MOF is more porous than Zn-MOF. Magnetic measurements on Co-MOF indicate a significant antiferromagnetic interaction (45 K to 303 K) between trimeric Co(II) S = 3/2 spins through syn-syn carboxylato bridges. Both MOFs were studied for the Lewis acid catalyzed Knoevenagel condensation reactions between benzaldehydes and malononitrile with an active methylene group, where Zn-MOF was found to be a better catalyst than Co-MOF. This was supported by the Monte Carlo simulations indicating the better substrate binding ability of Zn-MOF than Co-MOF.

Tandem Transformation of Indazolones to Quinazolinones through Pd-Catalyzed Carbene Insertion into an N-N Bond.

Serendipitous and expedite transformation of 1-aryl- and 2-aryl-1,2-dihydro-3H-indazol-3-ones to 1,2-di(hetero)aryl- and 2,3-di(hetero)aryl-2,3-dihydroquinazolin-4(1H)-ones, respectively, was achieved in high efficiency by reacting them with aldehydic N-tosylhydrazones. The protocol proceeded through a cascade process involving base-mediated Pd-carbenoid generation by the decomposition of N-tosylhydrazones, nucleophilic attack of indazolone on the Pd-carbenoid complex, and intramolecular ring expansion via N-N bond cleavage. The utility of the strategy is demonstrated toward the synthesis of bioactive NPS 53574, a calcium receptor antagonist.

Two Zn(II)/Cd(II) Coordination Polymers as Recyclable Heterogeneous Catalysts for an Efficient Room-Temperature Synthesis of α-Aminonitriles via the Solvent-Free Strecker Reaction.

The α-aminonitriles are versatile building blocks in the synthesis of natural or artificial amino acids as well as important intermediates in organic synthesis. For their synthesis, the three-component Strecker reaction involving an aldehyde or a ketone together with amines and trimethylsilyl cyanide is used. In the literature, hydrothermally produced metal-based heterogeneous Lewis acid catalysts have been utilized in various solvents. In this work, we aimed at a greener approach toward such catalysis by (a) making two precatalysts with d10 metal centers, {[Zn(hipamifba)(H2O)]·2H2O}n (1) and {[Cd(hipamifba)(H2O)2]·2H2O}n (2) (where H2hipamifba = 4-(((4-((carboxymethyl) carbamoyl)phenyl)amino)methyl)benzoic acid), via an easy and scalable room-temperature method, and (b) showcasing the use of these coordination polymers (CPs) as very efficient, recyclable, and heterogeneous catalysts for the Strecker reaction to form α-aminonitriles in high yields under solvent-free reaction at ambient conditions. This has also allowed us to demonstrate the importance of open metal sites in such catalysis through an efficiency comparison between activated 1 and 2. In addition, activated 2 exhibited a wide substrate scope including a natural product Girgensohnine, providing an example of a natural product synthesis by a CP catalyst via an organic transformation such as the Strecker reaction.

Effect of the flexible chain length of a dimetal subunit on the formation of 1D coordination polymers to molecular rectangles.

Utilizing the angular and rigid furan dicarboxylate (fdc2-) ion, a new series of four (1-4) metal-organic coordination networks (MOCNs) is synthesized in good yields through a one-pot self-assembly reaction in methanol under ambient conditions to demonstrate the effect of Cu2 dimetal subunits, connected by flexible polypyridyl bis(tridentate) ancillary ligands, tpxn, where x refers to the number of methylene groups connecting the alkyl nitrogen atoms in the ancillary ligands and is equal to 2, 4, 6, and 7. The solid-state molecular structures of 1-4 are determined by single-crystal X-ray diffraction. A change in the dimensionality of the resultant MOCN is observed from a 1D coordination polymer (CP) for 1, 2, and 3 to a molecular rectangle for 4. Furthermore, each unit of 4 contains one NaClO4. Using electrospray ionization (ESI) mass spectrometry, their structural integrity in solution and their purity of existence as a single product are confirmed. Further characterization of 1-4 by FTIR and UV-vis (in solution and solid-state) spectroscopy, and FESEM and TEM is also reported. The presence of unsaturated metal centers in 1-4 provided an opportunity to compare their Lewis acid catalytic activities for the Knoevenagel condensation reaction of malononitrile with various aldehydes.

Topologically Driven Pore/Surface Engineering in a Recyclable Microporous Metal-Organic Vessel Decorated with Hydrogen-Bond Acceptors for Solvent-Free Heterogeneous Catalysis.

The use of metal-organic frameworks (MOFs) comprising custom-designed linkers/ligands as efficient and recyclable heterogeneous catalysts is on the rise. However, the topologically driven bifunctional porous MOFs for showcasing a synergistic effect of two distinct activation pathways of substrates (e.g., involving hydrogen bonding and a Lewis acid) in multicomponent organic transformations are very challenging. In particular, the novelty of such studies lies in the proper pore and/or surface engineering in MOFs for bringing the substrates in close proximity to understand the mechanistic aspects at the molecular level. This work represents the topological design, solid-state structural characterization, and catalytic behavior of an oxadiazole tetracarboxylate-based microporous three-dimensional (3D) metal-organic framework (MOF), {[Zn2(oxdia)(4,4'-bpy)2]·8.5H2O}n (1), where the tetrapodal (4-connected) 5,5'-(1,3,4-oxadiazole-2,5-diyl)diisophthalate (oxdia4-), the tetrahedral metal vertex (Zn(II)), and a 2-connected pillar linker 4,4'-bipyridine (4,4'-bpy) are unique in their roles for the formation, stability, and function. As a proof of concept, the efficient utilization of both the oxadiazole moiety with an ability to provide H-bond acceptors and the coordinatively unsaturated Zn(II) centers in 1 is demonstrated for the catalytic process of the one-pot multicomponent Biginelli reaction under mild conditions and without a solvent. The key steps of substrate binding with the oxadiazole moiety are ascertained by a fluorescence experiment, demonstrating a decrease or increase in the emission intensity upon interaction with the substrates. Furthermore, the inherent polarizability of the oxadiazole moiety is exploited for CO2 capture and its size-selective chemical fixation to cyclic carbonates at room temperature and under solvent-free conditions. For both catalytic processes, the chemical stability, structural integrity, heterogeneity, versatility in terms of substrate scope, and mechanistic insights are discussed. Interestingly, the first catalytic process occurs on the surface, while the second reaction occurs inside the pore. This study opens new ways to catalyze different organic transformation reactions by utilizing this docking strategy to bring the multiple components close together by a microporous MOF.

Ruthenium-catalyzed (spiro)annulation of N-aryl-2,3-dihydrophthalazine-1,4-diones with quinones to access pentacyclic spiro-indazolones and fused-cinnolines.

Ru(II)-catalyzed strategies were developed for the [4 + 1] and [4 + 2] oxidative coupling between N-aryl-2,3-dihydrophthalazine-1,4-diones and 1,4-benzoquinones, achieving spiro-indazolones and fused-cinnolines, respectively. Mild, aerobic and external oxidant-free conditions, as well as the use of a ruthenium catalyst for such (spiro)annulative strategies with quinones over reported Rh/Ir-catalyts, underline the rewards of the disclosed protocols.

Subtle Ligand Spacer Change in 2D Metal-Organic Framework Sheets for Dual Turn-On/Turn-Off Sensing of Acetylacetone and Turn-On Sensing of Water in Organic Solvents.

Metal-organic framework (MOF)-based sensors for the detection of various analyte molecules has been a subject of absolute importance. However, most of these sensors rely on the turn-off (quenching) transduction response, while those reporting turn-on response are very rare. In this article, we have synthesized two new MOF-based sensors, {[Zn2(oxdz)2(tpbn)]·14H2O}n (1) and {[Zn2(oxdz)2(tpxn)]·10H2O·2C2H5OH}n (2), via the self-assembly of Zn(II) metal ions, a fluorogenic oxdz2- linker, and bis(tridentate) ligands (tpbn and tpxn) under ambient conditions. Their formation from such a self-assembly process has been evaluated on the basis of the geometry around the five-coordinated Zn(II), preferential meridional binding of the bis(tridentate) ligands, and diverse binding of the carboxylate groups in oxdz2-. Although 1 and 2 are isostructural, a difference in the transduction mechanism for the sensing of acetylacetone in organic solvents (turn-on for 1 and turn-off for 2) is observed and can be attributed to the spacer in the bis(tridentate) ligands. We have demonstrated the competing effect of the nonradiative interactions and photoinduced electron transfer toward the sensing mechanism. The results are well-supported by the Fourier transform infrared spectroscopy study, intensity versus concentration plots, spectral overlap measurements, time-resolved fluorescence studies, and MM2 and density functional theory calculations. Furthermore, we have showcased the utilization of 1 for the sensing of trace amounts of water in organic solvents.

Effect of Unsaturated Metal Site Modulation in Highly Stable Microporous Materials on CO2 Capture and Fixation.

We have designed and synthesized two unprecedented microporous three-dimensional metal-organic frameworks, {[Cd6(TPOM)3(L)6]·12DMF·3H2O}n (1) and {[Zn2(TPOM)(L)2]·2DMF·H2O}n (2), based on a flexible quadritopic ligand, tetrakis(4-pyridyloxymethylene)methane (TPOM), and a bent dicarboxylic acid, 4,4'-(dimethylsilanediyl)bis-benzoic acid (H2L). The networks of 1 and 2 share a 4-c uninodal net NbO topology but exhibit different metal environments due to coordination preferences of Cd(II) and Zn(II). The Cd(II) center in 1 is six-coordinated, whereas the Zn(II) center in 2 is only four-coordinated, making the latter an unsaturated metal center. Such modulation of coordination atmosphere of metal centers in MOFs with the same topology is possible due to diverse binding of the carboxylate groups of L2-. Both 1 and 2 have relatively high thermal stability and exhibit permanent porosity after the removal of guest solvent molecules based on variable temperature powder X-ray diffraction and gas adsorption analysis. These materials exhibit similar gas adsorption properties, especially highly selective CO2 uptake/capture over other gases (N2 and CH4). However, because of the presence of an unsaturated Lewis acidic metal site, 2 acts as a very efficient heterogeneous catalyst toward the chemical conversion of CO2 to cyclic carbonates under mild conditions, whereas 1 shows very less activity. This work provides experimental evidence for the postulate that an unsaturated metal site in MOFs enhances adsoprtion of CO2 and promotes its conversion via the Lewis-acid catalysis.

Regiodivergent Synthesis of Cinnoline-Fused Indazolones through Pd-Catalyzed Annulation of 1-Arylindazolones with Allenoates.

A tender-hearted Pd(II)-catalyzed C-H activation of 1-arylindazolones followed by an oxidative [4 + 2] annulation reaction has been accomplished, engaging allenoates as annulating partners. Using this strategy, two different regioisomeric forms of cinnoline-fused indazolones possessing internal and exocyclic double bonds were synthesized in acetic acid and dioxane, respectively. Mild and aerobic conditions, avoiding the use of any metal-oxidant, highlights the rewards of this oxidative annulation protocol.

Metal-Free Triazine-Based 2D Covalent Organic Framework for Efficient H2 Evolution by Electrochemical Water Splitting.

Hydrogen evolution reaction (HER) by electrochemical water splitting is one of the most active areas of energy research, yet the benchmark electrocatalysts used for this reaction are based on expensive noble metals. This is a major bottleneck for their large-scale operation. Thus, development of efficient metal-free electrocatalysts is of paramount importance for sustainable and economical production of the renewable fuel hydrogen by water splitting. Covalent organic frameworks (COFs) show much promise for this application by virtue of their architectural stability, nanoporosity, abundant active sites located periodically throughout the framework, and high electronic conductivity due to extended π-delocalization. This study concerns a new COF material, C6 -TRZ-TFP, which is synthesized by solvothermal polycondensation of 2-hydroxybenzene-1,3,5-tricarbaldehyde (TFP) and 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris[(1,1'-biphenyl)-4-amine]. C6 -TRZ-TFP displayed excellent HER activity in electrochemical water splitting, with a very low overpotential of 200 mV and specific activity of 0.2831 mA cm-2 together with high retention of catalytic activity after a long duration of electrocatalysis in 0.5 m aqueous H2 SO4 . Density functional theory calculations suggest that the electron-deficient carbon sites near the π electron-donating nitrogen atoms are more active towards HER than those near the electron-withdrawing nitrogen and oxygen atoms.

Luminescent 2D Pillared-Bilayer Metal-Organic Coordination Networks for Selective Sensing of ReO4- in Water.

For the preference in nuclear energy, one of the high-level liquid waste materials in the form of pertechnetate anion (TcO4-) has become an environmental hazard due to its mobility into groundwater and soil. For its sequestration, numerous efforts have been reported in recent years. However, its selective sensing, even using its nonradioactive surrogate oxidizing perrhenate ion (ReO4-), in aqueous media is very limited. To develop novel materials for such a purpose, we have designed an amino acid-functionalized bent dicarboxylic acid, 4-(((4-((carboxymethyl)carbamoyl)phenyl)amino)methyl)benzoic acid (H2hipamifba), for the strategic room-temperature synthesis of two isostructural and highly luminescent two-dimensional (2D) metal-organic coordination networks (MOCNs), {[Cu(hipamifba)(4,4'-azbpy)]·2CH3OH·2H2O}n (1) and {[Zn(hipamifba)(4,4'-azbpy)]·2CH3OH·2H2O}n (2), where 4,4'-azobipyridine (4,4'-azbpy) as a pillar linker imparts luminescent properties in the architectures. The single-crystal X-ray structural analysis demonstrates that 1 and 2 have pillared-bilayer 2D networks with the sq1/Shubnikov tetragonal plane net topology. These multiresponsive luminescent materials were gainfully employed for the selective sensing of ReO4- in water with a detection limit of 3.4 and 5.4 ppm for 1 and 2, respectively. It is noteworthy to point out that these are the first neutral sensors for such study as the only other two sensors reported in the literature are cationic in nature. Their suitability (selectivity, stability, and recyclability) as excellent water-stable sensors was established through the competitive analyte test and a comparison of pristine and spent samples by powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). Further, the mechanism of selective detection is explained by the time-resolved studies and density functional theory (DFT) calculations.