Rapid Suzuki‐Miyaura cross‐coupling reaction catalyzed by zirconium carboxyphosphonate supported mixed valent Pd(0)/Pd(II) catalyst

Mixed valent Pd(0)/Pd(II) nano‐sized aggregates supported onto a chemically robust layered zirconium carboxyphosphonate framework is prepared and its catalytic activity in Suzuki‐Miyaura cross coupling reaction is explored. The exceptionally high catalytic efficacy of the heterogeneous catalyst in Suzuki‐Miyaura cross coupling reaction is signified by remarkably short reaction time 2 minutes and high turnover frequency of 1.3 x 10⁴ hr^?1. The catalyst can be recycled several times without significant loss of catalytic efficacy, while spectroscopic, structural and microscopic investigations suggest the integrity of the catalyst even after fifth catalytic cycle. The unique ability of the zirconium carboxyphosphonate framework to interact strongly with palladium in dual Pd(0)/Pd(II) oxidation states has been attributed to this remarkable augmentation of catalytic efficacy.     

Through-Space Spin Coupling in a Silver(II) Porphyrin Dimer upon Stepwise Oxidations: AgII⋅⋅⋅AgII,AgII⋅⋅⋅AgIII,and AgIII⋅⋅⋅AgIII Metallophilic Interactions

Metallophilic interactions between closed-shell metal ions are becoming a popular tool for a variety of applications related to high-end materials. Heavier d⁸ transition-metal ions are also considered to have a closed shell and can be involved in such interactions. There is no systematic investigation so far to estimate the structure and energy characteristics of metallophilic interactions in Ag^II/Ag^II (d⁹/d⁹), Ag^III/Ag^III (d⁸/d⁸), and mixed-valent Ag^II/Ag^III (d⁹/d⁸) complexes, which have been demonstrated in the present study. Both interporphyrinic and intermetallic interactions were investigated on stepwise oxidation by using a rigid ethene-bridged cis silver(II) porphyrin dimer and the results compared with those for highly flexible ethane-bridged analogues. By controlling the nature of chemical oxidants and their stoichiometry, both 1e and 2e oxidations were done stepwise to generate Ag^II/Ag^III mixed-valent and Ag^III/Ag^III porphyrin dimers, respectively. Unlike all other ethene-bridged metalloporphyrin dimers reported earlier, in which 2e oxidation stabilizes only the trans form, such an oxidation of silver(II) porphyrin dimer stabilizes only the cis form because of the metallophilic interaction. Besides silver(II) ⋅⋅⋅ silver(II) interactions in cis silver(II) porphyrin dimer, stepwise oxidations also enabled us to achieve various hitherto-unknown silver(II) ⋅⋅⋅ silver(III) and silver(III) ⋅⋅⋅ silver(III) interactions, which thereby allow significant modulation of their structure and properties. The strength of Ag ⋅⋅⋅ Ag interaction follows the order Ag^II/Ag^II (d⁹/d⁹)<Ag^II/Ag^III (d⁹/d⁸)<Ag^III/Ag^III (d⁸/d⁸). Single-crystal XRD, X-ray photoelectron spectroscopy (XPS), ¹H NMR and EPR spectroscopy, and variable-temperature magnetic investigations revealed various oxidation states of silver and metallophilic interactions, which are also well supported by computational analysis.     

Spectroscopic Investigation of Tungsten Ions in Lead Scandium Phosphate Glass System

Lead scandium phosphate glasses (PbO-Sc₂O₃-P₂O₅) containing different concentrations of tungsten oxide (WO₃) ranging from 0 to 5 mol% were prepared. A number of studies, viz. differential thermal analysis (DTA), infrared spectra, optical absorption, and electron spin resonance (ESR) spectra, have been carried out. The results of DTA indicated the highest glass forming ability for the glass containing 5 mol% of WO₃. The results of spectroscopic studies have been analyzed in light of different oxidation states of tungsten ions.     

Size dependent structural and magnetic behaviour of CaFe2O4

CaFe₂O₄ nanocrystalline powders were synthesized through sol–gel treatment in which the stoichiometric mixing of various nitrates involving calcium and iron in presence of citric acid was performed. Subsequently, the as prepared sample was annealed at various temperatures in order to obtain the fine distribution of size including the bulk counterpart. The samples were then characterized using powder X-ray diffraction followed by ⁵⁷Fe Mössbauer spectroscopy, SQUID as well as vibrating sample magnetometry. The results of spectroanalyses revealed that the samples were formed in single phase cubic spinel structure and exhibits room temperature superparamagnetism, except the bulk one, which crystallizes in characteristic orthorhombic structure of CaFe₂O₄ and displays trivial coercivity and remanent magnetization at room temperature.     

Crystal structure of a cholesterol-based dimesogen

The title compound, cholesteryl 6[4-(4-pentyloxyphenylethynyl)phenoxy]hexanoate (DMT5), a cholesterol-based dimesogen, crystallizes in the monoclinic space group P2₁ with the parameters a = 9.812(3) Å, b = 9.713(2) Å, c = 24.179(2) Å, β = 92.48(1)° V = 2302.2(9) ų, Z = 2, F₀₀₀ = 836, λ(MoK_α) = 0.71069 Å, μ = 0.067 cm 1, final R = 0.0772. The structure has intermolecular hydrogen bonds; it is stabilized by the presence of intermolecular contacts whose spacings are less than van der Waals' radii.     

Sulfonated rGO from waste dry cell graphite rod and its hybrid with PANI as electrode for supercapacitor

Journal of Solid State Electrochemistry - Development of high-performance energy storage devices is a vital research area to meet the present-day energy demand. In the work carried toward the...     

Solution-processed electrochemical synthesis of ZnFe2O4 photoanode for photoelectrochemical water splitting

Journal of Solid State Electrochemistry - Herein, we report the synthesis of ZnO nanorod films onto FTO (fluorine-doped tin oxide) substrates using the solution-processed electrodeposition method....