Intercalating a potassium-aqua complex cation into an α-MoO3 layer without reducing molybdenum: a potential storage system.

We have demonstrated a green aqueous synthesis of rod-shaped MoO3 material, [MoVI3O9{K(H2O)4}(CH3COO)]·H2O (2) intercalating potassium-aqua-complex acetate into its lamellar space, simply by ion-exchange of Co(II)-aqua-complex in compound [MoVI4O12(CH3COO)2{CoII(H2O)6}]·2H2O (1) by {K(H2O)4}+ in an aqueous solution of 1 and KCl. Compound 2 acts as a potential storage system of alkali metal ions.

Electrocatalytic Hydrogen Evolution by a Uranium(VI) Polyoxometalate: an Environmental Toxin for Sustainable Energy Generation.

The uranyl ion (UO2)2+, a uranium nuclear waste, is one of the serious contaminants in our ecosystem because of its radioactivity, relevant human activities, and highly mobile and complex nature of living cells. In this article, we have reported the synthesis and structural characterization of an uranyl cation-incorporated polyoxometalate (POM) compound, K10[{K4(H2O)6}{UO2}2(α-PW9O34)2]·13H2O (1), in which the uranyl cations are complexed with an in situ generated [α-PW9O34]9- cluster. Single-crystal X-ray diffraction (SCXRD) analysis of compound 1 reveals that the uranyl-potassium complex cationic species, [{K4(H2O)6}{UO2}2]8+, is sandwiched by two [α-PW9O34]9- clusters resulting in a Dawson type of POM. Compound 1 was further characterized by inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis and infrared (IR), Raman, electronic absorption, and solid-state photoluminescence spectral studies. IR stretching vibrations at 895 and 856 cm-1 and the Raman signature peak at 792 cm-1 in the IR and Raman spectra of compound 1 primarily confirm the presence of a trans-[O═U═O]2+ ion. The solid-state photoluminescence spectrum of 1 exhibits a typical vibronic structure, resulting from symmetrical vibrations of [O═U═O]2+ bands, corresponding to the electronic transitions of S11 → S10 and S10 → S0υ (υ = 0-3). Interestingly, title compound 1 shows efficient electrocatalytic hydrogen evolution by water reduction with low Tafel slope values of 186.59 and 114.83 mV dec-1 at 1 mA cm-2 along with optimal Faradaic efficiency values of 82 and 87% at neutral pH and in acidic pH 3, respectively. Detailed electrochemical analyses reveal that the catalytic hydrogen evolution reaction (HER) activity mediated by compound 1 is associated with the UVI/UV redox couple of the POM. The microscopic as well as routine spectral analyses of postelectrode samples and controlled experiments have confirmed that compound 1 behaves like a true molecular electrocatalyst for the HER. To our knowledge, this is the first paradigm of a uranium-containing polyoxometalate that exhibits electrocatalytic water reduction to molecular H2. In a nutshell, an environmental toxin (a uranium-oxo compound) has been demonstrated to be utilized as an efficient electrocatalyst for hydrogen generation from water, a green approach of sustainable energy production.

Hydroxylated Polyoxometalate with Cu(II)- and Cu(I)-Aqua Complexes: A Bifunctional Catalyst for Electrocatalytic Water Splitting at Neutral pH.

A sole inorganic framework material [Li(H2O)4][{CuI(H2O)1.5} {CuII(H2O)3}2{WVI12O36(OH)6}]·N2·H2S·3H2O (1) consisting of a hydroxylated polyoxometalate (POM) anion, {WVI12O36(OH)6}6-, a mixed-valent Cu(II)- and Cu(I)-aqua cationic complex species, [{CuI(H2O)1.5}{CuII(H2O)3}2]5+, a Li(I)-aqua complex cation, and three solvent molecules, has been synthesized and structurally characterized. During its synthesis, the POM cluster anion gets functionalized with six hydroxyl groups, i.e., six WVI-OH groups per cluster unit. Moreover, structural and spectral analyses have shown the presence of H2S and N2 molecules in the concerned crystal lattice, formed from "sulfate-reducing ammonium oxidation (SRAO)". Compound 1 functions as a bifunctional electrocatalyst exhibiting oxygen evolution reaction (OER) by water oxidation and hydrogen evolution reaction (HER) by water reduction at the neutral pH. We could identify that the hydroxylated POM anion and copper-aqua complex cations are the functional sites for HER and OER, respectively. The overpotential, required to achieve a current density of 1 mA/cm2 in the case of HER (water reduction), is found to be 443 mV with a Faradaic efficiency of 84% and a turnover frequency of 4.66 s-1. In the case of OER (water oxidation), the overpotential needed to achieve a current density of 1 mA/cm2 is obtained to be 418 mV with a Faradaic efficiency of 80% and turnover frequency of 2.81 s-1. Diverse electrochemical controlled experiments have been performed to conclude that the title POM-based material functions as a true bifunctional catalyst for electrocatalytic HER as well as OER at the neutral pH without catalyst reconstruction.

A Rearrangement Reaction to Yield a NH4 + Ion Driven by Polyoxometalate Formation.

Triethylamine is a volatile liquid and exists in the atmosphere in the gas phase. It is a hazardous air pollutant and identified as a toxic air contaminant. Thus, producing ammonia (a vital chemical for fertilizer production) from the vapor state of this toxic substance is a challenging task. Diffusion of the vapor of triethylamine, (C2H5)3N, into an acidified aqueous solution of sodium molybdate results in the formation of single crystals of compound [(C2H5)3NH]2[(C2H5)4N][NaMo8O26] (1). Notably, compound 1 includes a [(C2H5)4N]+ cation, even though the concerned reaction mixture was not treated with any tetraethylammonium salt. The formation of the [(C2H5)4N]+ cation from (C2H5)3N in an acidic aqueous medium is logically possible only when an ammonium cation (NH4 +) is formed in the overall reaction: 4(C2H5)3N + 4H+ = 3[(C2H5)4N]+ + [NH4]+. Although the resulting NH4 + cation (identified by Nessler's reagent test) is not included in the crystals of compound 1 as a cation, it can be made associated with a crown ether in the isolation of single crystals of compound [NH4⊂B15C5]3[PMo12O40]·B15C5 (2), (B15C5 = benzo-15-crown-5). Crystal structure analysis and 1H NMR studies of compound 2 have established the presence of an H-bonded NH4 + ion in compound 2, thereby established the rearrangement reaction.

Barrel-Shaped-Polyoxometalates Exhibiting Electrocatalytic Water Reduction at Neutral pH: A Synergy Effect.

Two copper-based barrel-shaped polyoxometalates (POMs), namely, [{H3O}4{Na6(H2O)22}][{CuI (H2O)3}2{CuII (H2O)}3{B-α-BiIIIWVI9O33}2]·7H2O (NaCu-POM) and Li4[{NH4}2{H3O}3{Li(H2O)5}][{CuII(SH)}{(CuIICuI1.5)(B-α-BiIIIWVI9O33)}2]·9H2O (LiCu-POM) have been synthesized and structurally characterized. The single-crystal X-ray diffraction analyses of NaCu-POM and LiCu-POM reveal the presence of penta- and hexa-nuclear copper wheels per formula units, respectively; these copper wheels are sandwiched between two lacunary Keggin anions {B-α-BiIIIWVI9O33}9- (BiW9) to form the barrel-shaped title POM compounds. In both the compounds NaCu-POM and LiCu-POM, the mixed-valent copper centers are present in their respective penta- and hexa-nuclear copper wheels, established by X-ray photoelectron spectroscopy (XPS) as well as by bond valence sum (BVS) calculations. Compound LiCu-POM additionally shows the presence of a sulfhydryl ligand (SH-), coordinated to one of the copper centers of its {Cu6}-wheel, that is expected to be generated from the in situ reduction of sulfate anion present in the concerned reaction mixture (lithium-ion in ammonia solution may be the reducing agent). Interestingly, the title compounds, NaCu-POM and LiCu-POM exhibit an efficient electrocatalytic hydrogen evolution reaction (HER) by reducing water at neutral pH. Detailed electrochemical studies including controlled experiments indicate that the active sites for this electrocatalysis are the W(VI) centers of the title compounds, not the copper centers. However, a relevant tri-lacunary Keggin cluster anion {PVWVI9O33}7- (devoid of copper ion) does not show comparable HER as shown by the title compounds. The intra-cluster cooperative interactions of the mixed-valent copper centers (CuII/CuI) with the tungsten centers (W6+) make the overall system electrocatalytically active toward water reduction to molecular hydrogen at neutral pH. High Faradaic efficiencies (89 and 92%) and turnover frequencies (1.598 s-1 and 1.117 s-1) make the title compounds NaCu-POM and LiCu-POM efficient catalysts toward electrochemical water reduction to molecular hydrogen.

Single Crystals of α-MoO3-Intercalated {Ni(H2O)6}2+ and Electrocatalytic Water Reduction: Toward a Class of Molybdenum Bronzes.

We have successfully intercalated {NiII(H2O)6}2+ into the α-MoO3 layer, leading to the isolation of green single crystals of [MoVI2O6(CH3COO){NiII(H2O)6}0.5]·H2O (1). The homogeneous electrochemistry of 1 in its aqueous solution exhibits electrocatalytic hydrogen evolution reaction (HER) with concomitant electrochemical deposition of [HMo3VIMoVO12(CH3COO){NiII(H2O)5(OH)}] (2). Compound 2, a new molybdenum bronze, acts as an efficient and stable heterogeneous electrocatalyst for water reduction to molecular hydrogen. This work represents the first paradigm of a molybdenum bronze intercalating a transition metal-aqua ion.

Efficient homogeneous electrocatalytic hydrogen evolution using a Ni-containing polyoxometalate catalyst.

NiCl2·6H2O ([Ni(H2O)6]2Cl2) per se does not show electrocatalytic hydrogen evolution reaction activity (HER) in an acidic aqueous medium as well as in neutral water. Interestingly, when [Ni(H2O)6]2+ is present in a polyoxovanadate matrix, for example, in the compound K2[Ni(H2O)6]2[V10O28]·4H2O (1), it exhibits homogeneous electrocatalytic HER activity in an acidic aqueous solution with a turn over frequency of 2.1 s-1 and an effective low overpotential of 127 mV at pH 2.3. Compound 1 is the first nickel-containing polyoxometalate catalyst for hydrogen production via homogeneous electrocatalytic proton reduction without its decomposition under electrochemical conditions of HER.

Nanoblackberries of {W72Fe33} and {Mo72Fe30}: Electrocatalytic Water Reduction.

The reversible self-assembly of a {Mo72Fe30} cluster into nanoblackberries in a dilute solution of the relevant crystalline compound [Mo72Fe30O252(CH3COO)12{Mo2O7(H2O)}2{H2Mo2O8(H2O)}(H2O)91]·150H2O ({Mo72Fe30}cryst) was demonstrated by Liu, Müller, and their co-workers as a landmark discovery in the area of polyoxometalate chemistry. We have described, in the present work, how these ∼2.5 nm nano-objects, {M72Fe30} (M = W, Mo) can be self-assembled into nanoblackberries irreversibly, leading to their solid-state isolation as the nanomaterials Fe3[W72Fe30O252(CH3COO)2(OH)25(H2O)103]·180H2O ({W72Fe33}NM) and Na2[Mo72Fe30O252(CH3COO)4(OH)16(H2O)108]·180H2O ({Mo72Fe30}NM), respectively (NM stands for nanomaterial). The formulations of these one-pot-synthesized nanoblackberries of {W72Fe33}NM and {Mo72Fe30}NM have been established by spectral analysis including Raman spectroscopy, elemental analysis including ICP metal analysis, volumetric analysis (for iron), microscopy techniques, and DLS studies. The thermal stability of the tungsten nanoblackberries {W72Fe33}NM is much higher than that of its molybdenum analogue {Mo72Fe30}NM. This might due to the extra three ferric (Fe3+) ions per {W72Fe30} cluster in {W72Fe33}NM, which are not part of the {W72Fe30} cluster cage but are placed between two adjacent clusters (i.e., each cluster has six surrounding 0.5Fe3+) to form this self-assembly. The isolated blackberries behave like an inorganic acid, a water suspension of which shows pH values of 3.9 for {W72Fe33}NM and 3.7 for {Mo72Fe30}NM because of the deprotonation of the hydroxyl groups in them. We have demonstrated, for the first time, a meaningful application of these inexpensive and easily synthesized nanoblackberries by showing that they can act as electrocatalysts for the hydrogen evolution reaction (HER) by reducing water. We have performed detailed kinetic studies for the electrocatalytic water reduction catalyzed by {W72Fe33}NM and {Mo72Fe30}NM in a comparative study. The relevant turnover frequencies (TOFs) of {W72Fe33}NM and {Mo72Fe30}NM (∼0.72 and ∼0.45 s-1, respectively), the overpotential values of {W72Fe33}NM and {Mo72Fe30}NM (527 and 767 mV, respectively at 1 mA cm-2), and the relative stability issues of the catalysts indicate that {W72Fe33}NM is reasonably superior to {Mo72Fe30}NM. We have described a rationale of why {W72Fe33}NM performs better than {Mo72Fe30}NM in terms of catalytic activity and stability.

Devising a Polyoxometalate-Based Functional Material as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction.

Hydrogen is the solution to all the problems associated with the energy crisis. Generating hydrogen from water splitting is one of the greener approaches, but it requires an efficient catalyst that is economical for the bulk production of hydrogen. The transition metal-aqua coordination complexes, which are otherwise inactive/unstable for electrochemical hydrogen evolution reaction (HER) activity, can efficiently be utilized for the same by attaching these metal-aqua species on a stable support. With a similar approach, we have synthesized and structurally characterized a two-dimensional polyoxometalate (POM)-copper complex hybrid that supports a copper(II)-aqua-bypyridine complex with a molecular formula of the overall system, [{CuII(2,2'-bpy)(H2O)2}][{CoIIWVI12O40}{CuII(2,2'-bpy)(H2O)}{CuII(2,2'-bpy)}]·2H2O (1). The bis(aqua)-mono(bipyridine) Cu(II)-complex fragment {CuII(2,2'-bpy)(H2O)2}2+, attached to the two-dimensional POM-Cu-complex support, acts as an active catalytic center that catalyzes the electrochemical HER. The electrochemical studies done for this work enabled us to understand the role of compound 1 as an electrocatalyst for the HER in near-neutral medium (pH 4.8), under buffered conditions (acetate buffer). Through detailed electrochemical experiments including controlled ones, we understand that compound 1 follows a proton-coupled electron transfer (PCET) pathway with one proton and one electron involvement in the HER. The overpotential required to achieve a current density of 1 mA/cm2 is found to be 520 mV with a Faradaic efficiency of 81%.

Evolution of metal organic frameworks as electrocatalysts for water oxidation.

In the last two decades, metal organic frameworks (MOFs) have been extensively investigated to develop heterogeneous electrocatalysts for water oxidation (WO). The scope of reticular synthesis, enormous surface area and accessible internal volume of MOFs make them promising candidates for catalysis. However, low electrical conductivity, slow mass transport and lack of stability restrict the scope of MOF-based WO. In recent times, various material designing approaches, e.g., the introduction of mixed metal and multi-metal systems, ligand engineering, guest@MOF composite formation, preparation of thin films, MOF composite formation with conducting carbon-based materials, metal oxides, polymers and layered compounds, etc. have emerged as an effective means to counteract the aforementioned limitations. This feature article critically discusses the common MOF-based material designing strategies with respect to electrochemical WO and provides a platform to understand the potential of MOFs to prepare a sophisticated hybrid electrocatalyst for WO.

Efficient Electrocatalytic Water Oxidation by Fe(salen)-MOF Composite: Effect of Modified Microenvironment.

An efficient and robust heterogeneous electrocatalyst, FSWZ-8 ((Fe-(salen)(OH) + H4[SiW12O40]·HCl)@ZIF-8) for oxygen evolution reaction (OER) at the neutral pH, was developed by coencapsulation of Fe-salen (i.e., Fe(salen)Cl) and SiW12 (i.e., H4[SiW12O40]) inside the cavity of zeolitic imidazolate framework-8 (ZIF-8) material by an in situ synthesis. Here ZIF-8 functions as a host, Fe-salen as the active catalyst, and SiW12 helps in the charge transport by lowering the overall electrical resistance of the resulting composite system. High turnover frequency (∼5 s-1) and high Faradaic efficiency (∼94%) make the concerned composite an efficient catalyst toward water oxidation. This is the first report of one of the simplest known metal complexes, Fe-salen, to perfrom electrocatalytic OER as a heterogeneous catalyst in the neutral pH. This work also highlights the benefits of coencapsulation of the Keggin polyoxometalate (POM) along with the active catalyst Fe-salen species. Encapsulation of SiW12 results in (i) faster formation of FSWZ-8 composite, (ii) higher loading of Fe-salen, and, most importantly, (iii) lowering of required overpotential for electrochemical OER by more than 150 mV. The Keggin POMs, located as discrete molecular oxides inside the cavity of ZIF-8 as well as on the surface of ZIF-8, facilitate electrical charge conduction in the ZIF-8 matrix and lower the overall charge-transfer resistance.

Mononuclear Ru(II) Complexes of an Arene and Asymmetrically Substituted 2,2'-Bipyridine Ligands: Photophysics, Computation, and NLO Properties.

By using monosubstituted 2,2'-bipyridine asymmetric ancillary ligands with different electron donor moieties and an arene ligand (p-cymene), we successfully designed and synthesized six Ru(II) compounds (RuBPY1-6) that belong to a piano-stool-type system. The NLO properties of the synthesized complexes have been studied in both solution and the solid state. The electronic spectra of these compounds show a broad feature with two absorption bands in the visible window (350-650 nm). RuBPY1-6 complexes exhibit NIR emission spectra in the solution state (at >720 nm), the maxima of which are bathochromically shifted in comparison to those of the concerned ligands. Interestingly, compounds RuBPY1-6 show NIR emission in their solid state too. Title compounds RuBPY1-6 have lifetimes in the range of 0.2 to 0.9 ns. An important feature of this work is the π-association of the p-cymene ligand to Ru(II) in the synthesized complexes; the π complex is formed by breaking the symmetry of p-cymene, found in the starting precursor (Ru2 dimer). This has been established by NMR spectral studies along with DFT calculations on the 1H NMR spectra. We could derive the molecular structure of the cationic part of this system by density functional theory (DFT), associated with 1H NMR spectral studies. The minimum energy structures for RuBPY1 and RuBPY2 have been optimized at DFT/B3LYP along with the LANL2DZ basis set for ruthenium atoms. These optimized structures are further considered to calculate the excited state properties using the TDDFT method. The electrochemical studies of the complexes, investigated in acetonitrile solution, show that this system is associated with a well-defined Ru(III)/Ru(II) reversible couple, rarely observed for a Ru(II) piano-stool-type compound, along with a feature of irreversible ligand oxidation. The absorption cross-section values, obtained from the two-photon absorption studies of title compounds RuBPY1-6, are worth reporting and lie in the range of 3-28 GM (in the femtosecond case).

Carbonate encapsulation from dissolved atmospheric CO2 into a polyoxovanadate capsule.

An aqueous synthesis, involving the reduction of the VO3- anion in a mild alkaline pH in the presence of α-Bi2O3, led to the formation of a fully reduced polyoxovanadate (POV) capsule, with CO32- anion encapsulation in its internal cavity, in the compound [Na6(H2O)24][H8VO36(CO3)]·3N2H4·10H2O (1). This CO32- anion encapsulation, the source of which is absorbed aerial CO2 in the pertinent aqueous alkaline reaction mixture, occurs only in the presence of α-Bi2O3. Compound 1 crystals, upon exposure to HCl acid vapor, exclude CO2 gas that can react with the Grignard reagent (PhMgBr) to form triphenylcarbinol and benzoic acid; during this solid-vapor interface reaction, compound 1 itself transforms into an amorphous material that includes the Cl- anion but could not be characterized unambiguously. Thus, we have synthesized a chloride ion (Cl-) encapsulated compound [Na10(H2O)24][H3VO36(Cl)]·6H2O (2) in a direct synthesis protocol, which has been characterized by crystallography as well as by other spectroscopic methods. Compounds 1 and 2, each having fifteen vanadium(iv) centers, exhibit interesting magnetism in their solid states. The temperature-dependent magnetic susceptibilities for compounds 1 and 2 have been recordred at 0.1 T in the temperature range of 3-300 K. The temperature-dependent magnetic susceptibilities of compounds 1 and 2 are shown in the form of χMvs. T and their product χMT vs. T plots.

Designing UiO-66-Based Superprotonic Conductor with the Highest Metal-Organic Framework Based Proton Conductivity.

Metal-organic framework (MOF) based proton conductors have received immense importance recently. The present study endeavors to design two post synthetically modified UiO-66-based MOFs and examines the effects of their structural differences on their proton conductivity. UiO-66-NH2 is modified by reaction with sultones to prepare two homologous compounds, that is, PSM 1 and PSM 2, with SO3H functionalization in comparable extent (Zr:S = 2:1) in both. However, the pendant alkyl chain holding the -SO3H group is of different length. PSM 2 has longer alkyl chain attachment than PSM 1. This difference in the length of side arms results in a huge difference in proton conductivity of the two compounds. PSM 1 is observed to have the highest MOF-based proton conductivity (1.64 × 10-1 S cm-1) at 80 °C, which is comparable to commercially available Nafion, while PSM 2 shows significantly lower conductivity (4.6 × 10-3 S cm-1). Again, the activation energy for proton conduction is one of the lowest among all MOF-based proton conductors in the case of PSM 1, while PSM 2 requires larger activation energy (almost 3 times). This profound effect of variation of the chain length of the side arm by one carbon atom in the case of PSM 1 and PSM 2 was rather surprising and never documented before. This effect of the length of the side arm can be very useful to understand the proton conduction mechanism of MOF-based compounds and also to design better proton conductors. Besides, PSM 1 showed proton conductivity as high as 1.64 × 10-1 S cm-1 at 80 °C, which is the highest reported value to date among all MOF-based systems. The lability of the -SO3H proton of the post synthetically modified UiO-66 MOFs has theoretically been determined by molecular electrostatic potential analysis and theoretical p Ka calculation of models of functional sites along with relevant NBO analyses.

A Versatile Polyoxovanadate in Diverse Cation Matrices: A Supramolecular Perspective.

A series of decavanadate based compounds, formulated as [Co(H2O)6][{Na4(H2O)14}{V10O28}]·4H2O (1), [Zn(H2O)6][Na3(H2O)14] [HV10O28]·4H2O (2), [HMTAH]2 [{Zn(H2O)4}2{V10O28}]·2H2O (3), [{Co(3-amp)(H2O)5}]2 [3-ampH]2 [V10O28] · 6H2O (4), [4-ampH]10[{Na(H2O)6}{HV10O28}][V10O28]·15H2O (5), [{4-ampH}6 {Co(H2O)6}3][V10O28]2·14H2O (6), and [{4-ampH}10{Zn(H2O)6}][V10O28]2·10H2O (7), have been synthesized (where HMTAH = mono-protonated hexamethylenetetramine, 3-ampH = protonated 3-amino pyridine and 4-ampH= protonated 4-aminopyridine) from the relevant aqueous sodium-vanadate solution, by varying the pH of the solution and amino pyridine/hexamine derivatives as well as transition metal salts (Co(II)- and Zn(II)-salts). In this series of compounds 1-7, the polyoxovanadate (POV) cluster [V10O28]6- is the common cluster anion, stabilized by diverse cations. The diverse supramolecular patterns around the decavanadate cluster anion in different cationic matrices have been described to understand the microenvironment in the decavanadate-based minerals. All of these compounds have solvent water molecules in their respective crystal lattices. Since water can interact directly with cations and anions, providing an additional stability and structural diversity, we have analyzed supramolecular water structures in all these compounds to comprehend the role of the lattice water in the formation of natural decavanadate containing minerals. Compounds 1-7, that are isolated at an ambient condition from aqueous solution, are characterized by routine spectral analysis, elemental analyses and finally unambiguously by single crystal X-ray crystallography.

Polyoxometalate-Supported Bis(2,2'-bipyridine)mono(aqua)nickel(II) Coordination Complex: an Efficient Electrocatalyst for Water Oxidation.

A polyoxometalate (POM)-supported nickel(II) coordination complex, [NiII(2,2'-bpy)3]3[{NiII(2,2'-bpy)2(H2O)}{HCoIIWVI12O40}]2·3H2O (1; 2,2'-bpy = 2,2'-bipyridine), has been synthesized and structurally characterized. We could obtain a relatively better resolved structure from dried crystals of 1, NiII(2,2'-bpy)3]3[{NiII(2,2'-bpy)2(H2O)}{HCoIIWVI12O40}]2·H2O (D1). Because the title compound has been characterized with a {NiII(2,2'-bpy)2(H2O)}2+ fragment coordinated to the surface of the Keggin anion ([H(CoIIW12O40]5-) via a terminal oxo group of tungsten and the [NiII(2,2'-bpy)3]2+ coordination complex cation sitting as the lattice component in the concerned crystals, the electronic spectroscopy of compound 1 has been described by comparing its electronic spectral features with those of [NiII(2,2'-bpy)2(H2O)Cl]Cl, [NiII(2,2'-bpy)3]Cl2, and K6[CoIIW12O40]·6H2O. Most importantly, compound 1 can function as a heterogeneous and robust electrochemical water oxidation catalyst (WOC). To gain insights into the water oxidation (WO) protocol and to interpret the nature of the active catalyst, diverse electrochemical experiments have been conducted. The mode of action of the WOC during the electrochemical process is accounted for by confirmation that there was no formation/participation of metal oxide during various controlled experiments. It is found that the title compound acts as a true catalyst that has NiII (coordinated to POM surface) acting as the active catalytic center. It is also found to follow a proton-coupled electron-transfer pathway (two electrons and one proton) for WO catalysis with a high turnover frequency of 18.49 (mol of O2)(mol of NiII)-1 s-1.

Functional Molecular System of Bis(pyrazolyl)pyridine Derivatives: Photophysics, Spectroscopy, Computation, and Ion Sensing.

A new series of conjugated donor-π-acceptor type of 2,6-bis(pyrazolyl)pyridine derivatives (compounds IK-(3-9)) have been synthesized via Horner-Wadsworth-Emmons (HWE) reaction, starting from a common phosphonate precursor and diverse donor aromatic aldehydes and characterized by routine spectral analysis including elemental analysis. Compound IK-2, one of the starting precursors, and molecule IK-3, the first member of the donor-π-acceptor series, are additionally characterized by single-crystal X-ray structure determination. Compounds IK-2 and IK-3 are crystallized in P1̅ (triclinic) and P21/c (monoclinic) space groups, respectively. The absorption maxima in the electronic spectra of the title compounds shift mainly due to intramolecular charge transfer (ICT) between different donor (dibutyl and cyclic pyrrolidine) groups and the acceptor moiety [2,6-bis(pyrazolyl) pyridine]. Solution-state emission spectral studies of all these compounds show large solvent sensitive behavior with significant amounts of Stokes shifts. The large solvent dependence of the emission indicates that the excited state is stabilized in more polar solvents due to the ICT. All chromophores exhibit solid-state fluorescence behavior except compound IK-7. The role of the position and nature of the donor functionalities in the conjugated backbone of overall donor moiety of compounds IK-(3-9), on the electronic absorption properties of the title chromophores has been demonstrated, which has further been corroborated by density functional theory (DFT) and time-dependent DFT (TDDFT) computational studies. The emission spectral results of compounds IK-3, IK-5, and IK-7 have also been supported by the DFT and TDDFT calculations. A fluorescence lifetime study on this series also shows that the excited states are stabilized in more polar solvents. Finally, one of the chromophores (chromophore IK-4) in the title series has been shown to act as a selective molecular sensor (turn-off switch) for the Cu(II) ion.

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF-8, an Efficient and Robust Electrocatalyst.

Keggin-type polyoxometalate anions [XM12 O40 ]n- are versatile, as their applications in interdisciplinary areas show. The Keggin anion [CoW12 O40 ]6- turns into an efficient and robust electrocatalyst upon its confinement in the well-defined void space of ZIF-8, a metal-organic framework (MOF). [H6 CoW12 O40 ]@ZIF-8 is so stable to water oxidation that it retains its initial activity even after 1000 catalytic cycles. The catalyst has a turnover frequency (TOF) of 10.8 mol O2 (mol Co)-1 s-1 , one of the highest TOFs for electrocatalytic oxygen evolution at neutral pH. Controlled experiments rule out the chances of formation and participation of CoOx in this electrocatalyic water oxidation.

A Functional Zn(II) Metallacycle Formed from an N-Heterocyclic Carbene Precursor: A Molecular Sensor for Selective Recognition of Fe3+ and IO4- Ions.

We have reported the synthesis and structural characterization of a unique Zn(II) metallacycle (1) and its utilization as a fluorescent probe for the shape-specific selective recognition (turn-off) of Fe3+ and IO4- ions. The relevant Stern-Volmer graphs indicate that the recognitions of Fe3+ and IO4- ions are examples of diphasic and monophasic quenchings, respectively. The title metallacycle has been prepared by the reaction of a novel N-heterocyclic carbene precursor, 1,3-bis(2,6-diisopropyl-4-(pyridin-4-yl)phenyl)-1H-imidazol-3-ium chloride/bromide (L), and zinc(II) chloride salt. Notably, the ligand itself did not show any type of recognition for any ions. DFT calculations were performed on L and metallacycle 1 using the geometric parameters, obtained from their single-crystal X-ray diffraction data, to understand the electronic structures of the ligand and macrocycle. The detection limit for the recognition of the Fe3+ ion was determined to be 2.5 × 10-6 mol/L, and that for IO4- ion was found to be 6.3 × 10-5 mol/L.

Electrochemical Water Oxidation Catalyzed by an In Situ Generated α-Co(OH)2 Film on Zeolite-Y Surface.

The design and synthesis of an efficient and robust water-oxidation catalyst with inexpensive materials remains an important challenge in the context of artificial photosynthesis. Herein, a simple but unique technique is reported to in situ generate a thin-film of α-Co(OH)2 on the surface of zeolite-Y [hereafter referred to as Y-α-Co(OH)2 ] that acts as an efficient and stable catalyst for electrochemical water oxidation in alkaline medium. Catalyst Y-α-Co(OH)2 is so stable that it retains its catalytic activity even after 2000 cyclic voltammetric cycles of water oxidation. Expectedly, the chemical composition of α-Co(OH)2 on the surface of zeolite-Y remains same as that of parent Y-α-Co(OH)2 after 2000 electrocatalytic cycles. A Tafel slope as low as 59 mV decade-1 in 0.1 m KOH (pH 13) suggests faster oxygen evolution kinetics (overpotential=329 mV; turnover frequency=0.35 mol O2 (mol Co)-1 s-1 at 1 mA cm-2 ) than the existing α-Co(OH)2 -based electrocatalysts operating in alkaline medium.