Superior Electrochemical Water Splitting and Energy-Storage Performances of In Situ Fabricated Charge-Separated Metal Organophosphonate Single Crystals.

The design and exploration of advanced materials as a durable multifunctional electrocatalyst toward sustainable energy generation and storage development is the most perdurable challenge in the domain of renewable energy research. Herein, a facile in situ solvothermal approach has been adopted to prepare a methylviologen-regulated crystalline metal phosphonate compound, [C12H14N2][Ni(C11H11N2)(H2hedp)2]2•6H2O (NIT1), (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid) and well characterized by several techniques. The as-prepared NIT1 displays excellent bifunctional electrocatalytic activity with dynamic stability toward oxygen evolution reaction (η10 = 288 mV) and hydrogen evolution reaction (η10 = 228 mV) in alkaline (1.0 M KOH) and acidic mediums (0.5 M H2SO4), respectively. Such a low overpotential and Tafel slope (68 mV/dec for OER; 56 mV/dec for HER) along with long-term durability up to 20 h of NIT1 make it superior to benchmark the electrocatalyst and various nonprecious metal-based catalysts under similar experimental condition. Further, the electrochemical supercapacitor measurements (in three-electrode system) reveal that the NIT1 electrode possesses much higher specific capacity of 187.6 C g-1 at a current density of 2 A g-1 (272 C g-1 at 5 mV s-1) with capacitance retention of 75.2% over 10,000 cycles at 14 A g-1 (Coulombic efficiency > 99%) in 6 M KOH electrolyte medium. Finally for a practical application, an asymmetric supercapacitor device (coin cell) is assembled by NIT1 material. The as-fabricated device delivers the maximum energy density of 39.4 Wh kg-1 at a power density of 450 W kg-1 and achieves a wide voltage window of 1.80 V. Notably, the device endures a remarkable cycle performance with cyclic retention of 92% (Coulombic efficiency > 99%) even after 14,000 charge/discharge cycles at 10 A g-1. Nevertheless, the extraordinary electrochemical activities toward OER and HER as well as the high-performance device fabrication for LED illumination of such a noble metal-free lower-dimensional charge-transfer compound are truly path breaking and would be promising for the development of advanced multifunctional materials.

Intrinsic Specific Activity Enhancement for Bifunctional Electrocatalytic Activity toward Oxygen and Hydrogen Evolution Reactions via Structural Modification of Nickel Organophosphonates.

A comprehensive knowledge of the structure-activity relationship of the framework material is decisive to develop efficient multifunctional electrocatalysts. In this regard, two different metal organophosphonate compounds, [Ni(Hhedp)2]·4H2O (I) and [Ni3(H3hedp)2(C4H4N2)3]·6H2O (II) have been isolated through one-pot hydrothermal strategy by using H4hedp (1-hydroxyethane 1,1-diphosphonic acid) and N-donor auxiliary ligand (pyrazine; C4H4N2). The structures of synthesized materials have been established through single-crystal X-ray diffraction studies, which confirm that compound I formed a one-dimensional molecular chain structure, while compound II exhibited a three-dimensional extended structure. Further, the crystalline materials have participated as efficient electrocatalysts for the oxygen evolution and hydrogen evolution reactions (OER and HER) as compared to the state-of-the-art electrocatalyst RuO2. The electrocatalytic OER and HER performances show that compound II displayed better electrocatalytic performances toward OER (η10 = 305 mV) and HER (η10 = 230 mV) in alkaline (1 M KOH) and acidic (0.5 M H2SO4) media, respectively. Substantially, the specific activity has been assessed in order to measure the inherent electrocatalytic activity of the title electrocatalyst, which displays an enrichment of fourfold higher activity of compound II (0.64 mA/cm2) than compound I (0.16 mA/cm2) for the OER experiments. Remarkably, inclusion of an auxiliary pyrazine ligand into the metal organophosphonate structure (compound II) not only offers higher dimensionality along with significant enhancement of the overall bifunctional electrocatalytic performances but also improves the long-term stability, which is noteworthy for the family of hybrid framework materials.

1,2,3-Triazole-based esters and carboxylic acids as nonclassical carbonic anhydrase inhibitors capable of cathepsin B inhibition.

Herein, we report the design and synthesis of a library of 28 new 1,2,3-triazole derivatives bearing carboxylic acid and ester moieties as dual inhibitors of carbonic anhydrase (CA) and cathepsin B enzymes. The synthesised compounds were assayed in vitro for their inhibition potential against four human CA (hCA) isoforms, I, II, IX and XII. The carboxylic acid derivatives displayed low micromolar inhibition against hCA II, IX and XII in contrast to the ester derivatives. Most of the target compounds showed poor inhibition against the hCA I isoform. 4-Fluorophenyl appended carboxylic acid derivative 6c was found to be the most potent inhibitor of hCA IX and hCA XII with a KI value of 0.7 µM for both the isoforms. The newly synthesised compounds showed dual inhibition towards CA as well as cathepsin B. The ester derivatives exhibited higher % inhibition at 10-7 M concentration as compared with the corresponding carboxylic acid derivatives against cathepsin B. The results from in silico studies of the target compounds with the active site of cathepsin B were found in good correlation with the in vitro results. Moreover, two compounds, 5i and 6c, showed cytotoxic activity against A549 lung cancer cells, with IC50 values lower than 100 µM.

Macrocyclic Sulfur Ligand Stabilized Trans-Palladium Dichloride Complex: Syntheses, Structure, Chlorine Rotation, and Application in α-Olefination of Nitriles by Primary Alcohols.

Herein, we have reported the synthesis of a macrocyclic organosulfur ligand (L1) having a seventeen-membered macrocyclic ring. Subsequently, the corresponding trans-palladium complex (C1) of bulky macrocyclic organosulfur ligand (L1) was synthesized by reacting it with PdCl2 (CH3 CN)2 salt. The newly synthesized ligand and complex were characterized using various analytical and spectroscopic techniques. The complex showed a square planar geometry with trans orientation of two ligands around the palladium center. The complex possesses intramolecular SCH…Cl interactions of 2.648 Šbetween the macrocyclic ligand and palladium dichloride. The potential energy surface (PES) for the rotational process of C1 suggested a barrier of ~23.81 kcal/mol for chlorine rotation. Furthermore, the bulky macrocyclic organosulfur ligand stabilized palladium complex (C1) was used as a catalyst (2.5 mol %) for α-olefination of nitriles by primary alcohols. The α,ß-unsaturated nitrile compounds were found to be the major product of the reaction (57-78 % yield) with broad substrate scope and large functional group tolerance. Notably, the saturated nitrile product was not observed during the reaction. The mechanistic studies suggested the formation of H2 and H2 O as only by-products of the reaction, thereby making the protocol greener and sustainable.

Bifunctional Role of Methyl Viologen in UV and X-ray Sensitive Switchable Organophosphonate Single Crystal.

Finding X-ray and UV responsive hybrid single crystals including their versatile properties is highly desirable though the fabrication of such material is a very challenging task to researchers. Herein, a methyl viologen assisted hybrid nickel organophosphonate structure (i.e., NIT1) is demonstrated by adapting an in situ solvothermal strategy to investigate the X-ray effect and photochromic behaviors. The bifunctional coordinated and templated roles of monocationic and bicationic methyl viologen units present in the hybrid structure are noteworthy and can manifest prominent structural enhancement and reversible photochromism behaviors.

A palladium complex of a macrocyclic selenium ligand: catalyst for the dehydroxymethylation of dihydroxy compounds.

This report describes the synthesis of a seventeen-membered macrocyclic ring containing ligand (L1) by the reaction of 1,8-bis(2-(chloromethyl)phenoxy)octane with selenium powder. The trans-palladium dichloride complex (C1) of the macrocyclic selenium ligand was synthesized from its reaction with the Pd(CH3CN)2Cl2 precursor. The formation of the ligand and complex was authenticated with the help of various analytical techniques like 1H and 13C{1H} NMR, HRMS, FTIR, UV-visible spectroscopy, and elemental analysis. The structure of the ligand and its coordination mode with the palladium precursor were authenticated with the help of single crystal X-ray diffraction. The complex possesses a distorted square planar geometry around the palladium center. The new ligand and complex are air and moisture insensitive and stable at room temperature for over three months. The variable temperature NMR data and computational studies suggest selenium inversion in the palladium complex (C1) with an inversion barrier of ∼22.6 kcal mol-1. The palladium complex C1 was used as a catalyst for the dehydroxymethylation of long alkyl chain containing dihydroxy compounds. Generally, two separate catalysts are used for dehydroxymethylation (one for the oxidation of the alcohol and the other for the decarbonylation of the aldehyde). Here a single catalyst shows the dual action of dehydroxymethylation with up to 91% yield under only 5.0 mol% catalyst loading. A broad substrate scope can be achieved with good functional group tolerance. The PPh3 and Hg poisoning tests suggest the homogeneous nature of the reaction. Interestingly, the same long alkyl chain containing dihydroxy compounds were reported to undergo macrolactonization when reacted with a ruthenium catalyst.

Synthesis, antimicrobial, antibiofilm and computational studies of isatin-semicarbazone tethered 1,2,3-triazoles.

In present era, heterocyclic compounds containing two or three nitrogen atoms play a vital role in drug discovery. In this context, a new class of isatin-semicarbazone tethered 1,2,3-triazole hybrids was synthesized via Cu(I)-mediated azide alkyne cycloaddition reaction. Structural characteristics of the newly derived compounds were identified by various spectral techniques like FTIR, 1H NMR, 13C NMR, HRMS and single crystal X-ray crystallography. Synthesized derivatives were also screened for in vitro antimicrobial and antibiofilm activity against different microbial species. Triazole hybrid 7e showed significant efficacy towards E. coli having MIC of 0.0063 µmol/mL, whereas 6a, 6b, 7a, 7c, 7e, and 7f showed highest percentage of biofilm inhibition against P. aeruginosa. Bioassay results suggested that these triazole hybrids could act as biomaterial for antimicrobial and antibiofilm applications and may constitute a new promising class of antimicrobial and antibiofilm agents. These results were further supported by in silico docking, DFT calculations and ADME studies.

A multi-cation responsive Ni(II)-supramolecular metallogel mimics a molecular keypad lock via reversible fluorescence switching.

Synthesis of a bidentate N,O-donor Schiff base fluorescent ligand 5-(diethylamino-2-((4-(diethylamino-2-((4-(diethylamino)phenylimino)ethyl)phenol) (HL) adopting a new preparation procedure and its complexes with Ni(II) (1) and Zn(II) (2) has been illustrated. Structures of HL and 1 have been elucidated using X-ray single crystal analysis. Moreover, HL leads to the formation of a mechanically stable Ni(II)-gel (MG) upon treatment with Ni(NO3)2·6H2O in the presence of triethylamine (TEA) using THF/MeOH (1 : 1) solvents at rt. The gelator HL, complexes 1-2 and MG have been characterized by different spectroscopic and microscopic techniques including NMR (1H & 13C), FT-IR, ESI-MS, SEM, powder-XRD, rheology, UV/vis and fluorescence analysis. Rheological studies suggested good mechanical and thermal stability, whereas SEM analysis reveals a porous earth crust-like morphology of MG. Notably, 1 : 1 complexation between HL and Ni(II) forms a stable gel (MG), whereas 2 : 1 (HL : Ni2+) complexation leads to partial gelation. Formation of the Ni(II)-MG leads to slight "Turn-OFF" fluorescence relative to HL with a limit of detection (LOD) of 7.76 × 10-9 M; however, MG is considered as the "ON" state due to moderate emission. Remarkably, Ni(II)-MG further displayed reversible "ON-OFF-ON" fluorescence switching behavior through detection of Zn2+, Cu2+ and Hg2+. The emission intensity of MG is quenched with Cu2+/Hg2+ but enhances with Zn2+ in 1 : 1 (MG : M2+) stoichiometry. Therefore, MG mimics a sequence dependent molecular keypad lock for Cu2+ (C), Hg2+ (H) and Zn2+ (Z) to give the maximum output. Association and quenching constants were calculated by the Benesi-Hildebrand method, and from the Stern-Volmer plot the LOD was determined to be 4.2 × 10-6 M, 5.8 × 10-6 M and 7.8 × 10-6 M for MG with Zn(II), Cu(II) and Hg(II), respectively. To date, Ni(II) based MGs have been explored only toward electrochemical, thermal and conduction studies; however, the present work demonstrates the fluorescent reversible cation detection behavior of Ni(II)-MG to act as a molecular keypad lock for development of password protection devices.

Organoamine Templated Multifunctional Hybrid Metal Phosphonate Frameworks: Promising Candidates for Tailoring Electrochemical Behaviors and Size-Selective Efficient Heterogeneous Lewis Acid Catalysis.

The successful discovery of novel multifunctional metal phosphonate framework materials that incorporate newer organoamines and their utilization as a potential electroactive material for energy storage applications (supercapacitors) and as efficient heterogeneous catalysts are the most enduring challenges at present. From this perspective, herein, four new inorganic-organic hybrid zinc organodiphosphonate materials, namely, [C5H14N2]2[Zn6(hedp)4] (I), [C5H14N2]0.5[Zn3(Hhedp) (hedp)]·2H2O (II), [C6H16N2][Zn3(hedp)2] (III), and [C10H24N4][Zn6(Hhedp)2(hedp)2] (IV) (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid), have been synthesized through the introduction of different organoamines and then structurally analyzed using various techniques. The compounds (I-IV) possess a three-dimensional network through alternate connectivity of zinc ions and diphosphonate ligands, as confirmed using single-crystal X-ray diffraction. The investigations of electrochemical charge storage behaviors of the present compounds indicate that compound III exhibits a high specific capacitance of 190 F g-1 (76 C g-1) at 1 A g-1, while compound II shows an excellent cycling stability of 90.11% even after 5000 cycles at 5 A g-1 in the 6 M KOH solution. Further, the present materials have also been utilized as active heterogeneous Lewis acid catalysts in the ketalization reaction. The screening of various substrate scopes during the catalytic process confirms the size-selective heterogeneous catalytic nature of the framework compounds. To our utmost knowledge, such a size-selective heterogeneous Lewis acid catalytic behavior has been observed for the first time in the amine templated inorganic-organic hybrid framework family. Moreover, the excellent size-selective catalytic efficiencies with the d10 metal system and recyclability performances make the compounds (I-IV) more efficient and promising Lewis acid heterogeneous catalysts.

Antiferromagnetically coupled double perovskite as an efficient and robust catalyst for visible light driven water splitting at neutral pH.

Green and sustainable energy production through renewable sources is an enormously exciting field of research. Herein, we report an A-site lanthanum doped oxygen excess ruthenate (predominantly Ru5+-ions) double perovskite system, CaLaScRuO6+δ (CLSR), as an excellent photocatalyst for water splitting. The well characterized polycrystalline compound shows canted antiferromagnetic (AFM) behavior due to the existence of disordered Ru-ions at the B-site. Based on density functional theory + U (Hubbard U) calculations, we have estimated various magnetic exchange interactions and found that the ground state is antiferromagnetic in nature which is in perfect agreement with our experimental results. Detailed analysis of the electronic structure further reveals that the present system belongs to the family of charge transfer semiconductors with an energy gap of ∼0.45 eV. Finally, the material is found to proficiently work for the oxygen evolution reaction (OER) via visible-light driven water splitting at neutral pH in an ecofriendly manner.

Charge Separated One-Dimensional Hybrid Cobalt/Nickel Phosphonate Frameworks: A Facile Approach to Design Bifunctional Electrocatalyst for Oxygen Evolution and Hydrogen Evolution Reactions.

Two new organoamine templated one-dimensional transition metal phosphonate compounds are synthesized, and their bifunctional electrocatalytic activities are examined in highly alkaline and acidic media. Compared with state-of-the-art materials, the cobalt phosphonate system is a new fabrication of sustainable and highly efficient catalysts toward electrochemical water splitting systems.

Evolution of transition metal charge states in correlation with the structural and magnetic properties in disordered double perovskites Ca2-xLaxFeRuO6 (0.5 ≤ x ≤ 2).

A series of disordered Ca1.5La0.5FeRuO6, CaLaFeRuO6 and La2FeRuO6 double perovskites were prepared by the solid-state reaction method and investigated by neutron powder diffraction, X-ray absorption near-edge structure (XANES) analysis at the Ru-K edge, Mössbauer spectroscopy, DC magnetization and resistivity measurements. All compounds crystallize in the orthorhombic crystal structure with the space group Pbnm down to 3 K, showing a random distribution of Fe and Ru at the B site. Thermogravimetric analysis indicates oxygen deficiency in the Ca-rich and formal oxygen hyperstoichiometry in the La-rich members of the present series. While Mössbauer spectra verify the Fe3+ state for all compositions, the XANES study reveals a variable Run+ oxidation state which decreases with increasing La content. The end member actually is a Ru3+/Ru4+ compound with possibly some cation vacancies. From magnetic susceptibility and neutron diffraction measurements, the presence of a G-type antiferromagnetic ordering was observed with a drastic increase in transition temperature from 275 K (Ca1.5La0.5FeRuO6) to 570 K (La2FeRuO6). Mössbauer spectroscopy confirms the presence of long-range ordering but, due to local variations in the exchange interactions, the magnetic states are microscopically inhomogeneous. All the samples are variable range hopping semiconductors. A complex interplay between structural features, charge states, anion or cation defects, and atomic disorder determines the magnetic properties of the present disordered 3d/4d double perovskite series.

Role of aromatic vs. aliphatic amine for the variation of structural, electrical and catalytic behaviors in a series of silver phosphonate extended hybrid solids.

Four inorganic-organic hybrid silver phosphonate compounds, [Ag(C10H8N2)(H4hedp)] (1), [Ag2(C10H8N2)(H3hedp)]·2H2O (2), [C4H12N2][Ag4(H2hedp)2] (3) and [C4H12N2][Ag10(H2hedp)4(H2O)2]·2H2O (4) (H5hedp = 1-hydroxyethane-1,1-diphosphonic acid), have been prepared by virtue of the variable amine-directed hydrothermal strategy. The subsequent roles of coordinated aromatic amine (4,4'-bipyridine) and coordination-free templated aliphatic amine (piperazine) are studied. The connectivity of the silver ions, diphosphonate units (hedp) and bipyridine moiety can give rise to the one-dimensional structure of 1 and two-dimensional layer structure of 2. In contrast, the silver ions and diphosphonate units are connected to form the tetrameric and pentameric silver cluster units in compound 3 and 4, respectively. Such clusters are rare examples of fundamental building units in the piperazine templated two-dimensional silver based layer structures. The room temperature dielectric studies show the extremely high dielectric permittivity of the amine templated compounds (3 and 4) compared to amine coordinated structures (1 and 2). The synthesized compounds also participate in various heterogenous catalytic reactions acting as active Lewis acid catalysts that are observed for the first time in the amine-templated metal organophosphonates. The observed band gaps and dielectric values suggest that compounds 3 and 4 are more promising candidates for electronic applications, while compounds 1 and 2 are comparatively better Lewis acid catalysts.

Detailed characterization of dioxouranium(vi) complexes with a symmetrical tetradentate N2O2-benzil bis(isonicotinoyl hydrazone) ligand.

The reactions of UO2(OAc)2·2H2O with benzil bis(isonicotinoyl hydrazone) ligand (H2L) in varied solvent media resulted in the formation of a series of new dioxouranium(vi) complexes 1-3 of the type UO2(L)(X), [where 1, X = DMF; 2, X = DMSO; 3, X = H2O]. The complexes were systematically characterized by elemental analysis, UV-Visible spectroscopy, TGA, mass spectrometry, cyclic voltammetry, and powder X-ray diffraction study. Among all the complexes, 1 was confirmed by single-crystal X-ray diffraction study. It was found that 1 preferred a distorted pentagonal bipyramidal geometry, in which an equatorial coordination plane was formed by the ONNO-tetradentate cavity of the deprotonated hydrazone ligand along with an additional oxygen atom of the coordinated solvent molecule. Thermal analysis suggested that complexes 1 and 3 undergo weight loss in the temperature range 180-210 °C and 100-120 °C, respectively, due to the ready release of their coordinated solvent molecules. Complexes 1-3 exhibited analogous UV-Visible absorption bands and the intense band between 300-600 nm was assigned to the M ← L and n → π* transitions. Weakly resolved reduction waves assigned to {UO2}2+/{UO2}+ couple were observed for complexes 1 and 2 {1, -1.76 V; 2, -1.75 V; vs. ferrocenium/ferrocene (Fc+/Fc)} in DMSO solution, signifying the feeble electron-donating nature of the L2- ligand. Powder X-ray diffraction study suggested that the crystallite size of all the complexes was in the nanoscale range. Further analysis using density functional theory (DFT) calculations provided structural insights as well as information on the electronic properties of both complex 1 and the ligand.

Isatin as a 2-aminobenzaldehyde surrogate: transition metal-free efficient synthesis of 2-(2'-aminophenyl)benzothiazole derivatives.

A transition metal-free, convenient, and efficient practical approach has been devised for the synthesis of substituted 2-(2'-aminophenyl)benzothiazoles via a sulfur insertion strategy using isatin derivatives as 2-aminobenzaldehyde surrogates. KI assisted one-pot operation of isatin, arylamines and elemental sulfur resulted in the formation of a C-N and two C-S bonds and cascade cleavage of the isatin ring resulting in the formation of 2-(2'-aminophenyl)benzothiazoles. The significant features of this strategy are the readily available and inexpensive starting materials, broad substrate scope, sustainable reaction conditions and high yield of products. Importantly, the strategy was found to be appropriate for gram scale synthesis (>10 g) of 2-(2'-aminophenyl)benzothiazole derivatives. Moreover, the excellent photophysical properties (ΦF up to 60%) of 2-(2'-aminophenyl)benzothiazole derivatives provide huge scope in materials science.

Colossal Dielectric Responses from the Wide Band Gap 2D-Semiconducting Amine Templated Hybrid Framework Materials.

Two unprecedented organic amine templated silver organophosphonate hybrid solids have been synthesized hydrothermally by varying the molar ratio of the reactants. Both of the compounds consist of novel tetra- and penta-nuclear silver phosphonate basic building units. The dielectric constants are extremely large due to the charge separation of anionic metal phosphonate frameworks and cationic templated piperazine moieties in the compounds, as found for the first time in a hybrid organophosphate family. The conductivity and UV-visible absorption studies provide strong evidence about the semiconducting nature of the present compounds.

Investigation of New B-Site-Disordered Perovskite Oxide CaLaScRuO6+δ: An Efficient Oxygen Bifunctional Electrocatalyst in a Highly Alkaline Medium.

Energy storage and conversion driven by electro- or photocatalyst is a highly exciting field of research, and generations of effective and durable oxide catalysts have received much attention in this field. Here, we report A-site lanthanum-doped oxygen-rich quinary oxide CaLaScRuO6+δ synthesized by adopting the solid-state reaction method and characterized by various techniques such as powder X-ray diffraction, neutron diffraction, energy-dispersive X-ray spectroscopy, inductively coupled plasma-atomic emission spectrometry, Raman spectroscopy, and temperature-programmed reduction in the presence of a hydrogen atmosphere (H2-TPR). X-ray absorption study confirms the existence of mixed valent Ru ions in the structure, which enhances the oxygen stoichiometry for the partial balance of an extra cationic charge. Neutron powder diffraction and reduction of the material in a hydrogen atmosphere (H2-TPR) can confirm the oxygen overstoichiometry of the catalyst. The present material works as an efficient and robust oxygen bifunctional electrocatalyst for ORR/OER (oxygen evolution reaction/oxygen reduction reaction) followed by four-electron transfer pathway in a strong (1 M KOH) alkaline medium. The catalytic nature of the designed structural and chemical flexible perovskite is a novel example of an electrocatalyst for the oxygen bifunctional activity.

Triggering Lewis Acidic Nature through the Variation of Coordination Environment of Cd-Centers in 2D-Coordination Polymers.

The rational design and successful synthesis of novel functional metal-organic frameworks relies on careful selection of metals and versatile organic ligands. A newly designed pyrazole-based dicarboxylate ligand, 5-(3,5-dimethyl-1H-pyrazol-1-yl) 1,3-benzenedicarboxylic acid (H2L), was utilized to obtain two new Cd-based coordination polymers I [Cd(L)(H2O)]·H2O and II [Cd(L)] under similar reaction conditions via solvothermal strategy. Single-crystal X-ray data confirmed that compound I exhibits a two-dimensional (2D) skeleton comprising pentagonal bipyramidal Cd-ions and an organic ligand moiety. Compound II has also formed a two-dimensional layer arrangement with the connectivity between trigonal bipyramidal Cd-ions and the organic ligand. Topological analysis revealed that compound I has formed unique 43.63 net topology while compound II has displayed a 44.62 sql net topology with 2D frameworks. The Lewis acidic nature of both I and II containing a Cd2+ metal center has been correlated with the coordination number through dye adsorption-desorption and catalysis studies. The selective adsorption of anionic dye and the extent of adsorption are interrelated with the Cd-ion geometry. For the first time, the role of coordinated water molecule has been analyzed through heterogeneous catalysis reaction (i.e., cyanosilylation) with Cd-based 2D-coordination polymers (CPs). The plausible mechanisms have been proposed to explain the subsequent role of coordination number and environment in CPs.

Getting insights of molecular interactions for potential drug candidates against S. aureus: Pharmacophore modeling, molecular screening and docking studies.

There are a vast number of newly synthesized drugs against various pathogens in the last few decades but the problem still remains intact due to unempirical approaches to synthesize molecules without proper study on the target. This study focusses on development of a pharmacophore model through incorporating features from a wide variety of azole-based scaffolds (183 numbers) and thereby molecular screening from online available databases and libraries (10,89,394 molecules). Out of them, 6,04,696 molecules are filtered out through the pharmacophore-based virtual screening. These best discovered molecules are then docked against the target S. aureus DNA gyrase followed by interaction analysis and ADME as well as MM-GBSA studies, which led us to 23 best-hit compounds. After in silico analysis, best 10 molecules were predicted which exhibited excellent binding affinity as well as interactions against the target protein and some are even better than the well-known drug, ciprofloxacin. This study enables us to excavate pre-existing molecules, which have not been explored till date against this pathogenic strain of bacteria, but can definitely be used as alternatives to resistant drugs.

Crystal structure of bis-(piperazin-1-ium-κN4)bis-(thio-sulfato-κS)zinc(II) dihydrate.

In the title compound, [Zn(C4H11N2)2(S2O3)2]·2H2O, two thio-sulfate ions coordinate to the zinc(II) atom through the terminal S atoms. The tetra-hedral coordination around the ZnII ion is completed by ligating to two N atoms of two piperazinium ions. The remaining two N atoms of the piperazinium ions are diprotonated and do not coordinate to the metal centre. In the crystal, however, they are involved in N-H⋯Owater and N-H⋯Osulfato hydrogen bonds. Together, a series of N-H⋯O and O-H⋯O hydrogen bonds, involving the O atoms of the thio-sulfate ions and the water mol-ecules as acceptors and the hydrogen atoms of the piperazinium ions and the water mol-ecules as donors, form a three-dimensional supra-molecuar structure. Within this framework there are a number of intra- and inter-molecular C-H⋯O and C-H⋯S contacts present.