Synthesis,spectroscopic evaluation,molecular modelling,thermal study and biological evaluation of manganese(II) complexes derived from bidentate N,O and N,S donor Schiff base ligands

Manganese(II) complexes having the general composition Mn(L)₂X₂ (where L = 3‐bromoacetophenone semicarbazone, 3‐bromoacetophenone thiosemicarbazone, 1‐tetralone semicarbazone, 1‐tetralone thiosemicarbazone, flavanone semicarbazone or flavanone thiosemicarbazone and X = Cl^? or ½SO₄^2?) were synthesized. All the complexes were characterized using elemental analyses, molar conductance and magnetic moment measurements, and mass, ¹H NMR, infrared, electron paramagnetic resonance and electronic spectral studies. The molar conductance of the complexes in dimethylsulfoxide lies in the range 10–20 Ω^?1 cm² mol^?1 indicating their non‐electrolytic nature. All the complexes show magnetic moments corresponding to five unpaired electrons. The possible geometries of the complexes were assigned on the basis of electron paramagnetic resonance, electronic and infrared spectral studies. Some of the synthesized ligands and their complexes were screened for their antifungal activities against fungi Macrophomina phaseolina, Botrytis cinerea and Phoma glomerata using the food poison technique and their antibacterial activities against Xanthomonas campestris pv. campestris and Ralstonia solanacearum using the paper disc diffusion method. They showed appreciable activities.     

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.     

On the impulsive implicit Ψ-Hilfer fractional differential equations with delay

In this paper, we investigate the existence and uniqueness of solutions and derive the Ulam-Hyers-Mittag-Leffler stability results for impulsive implicit Ψ-Hilfer fractional differential equations with time delay. It is demonstrated that the Ulam-Hyers and generalized Ulam-Hyers stability are the specific cases of Ulam-Hyers-Mittag-Leffler stability. Extended version of the Gronwall inequality, abstract Gronwall lemma, and Picard operator theory are the primary devices in our investigation. We provide an example to illustrate the obtained results.     

Structural properties of rutherfordium: An ab-initio study

The structural and electronic properties of rutherfordium, the latest group IV B element, have been evaluated by first principles density functional theory in scalar relativistic formalism with and without spin-orbit coupling and compared with its 5d homologue Hf. It is found that Rf will crystallize in the hexagonal close packed structure as in Hf. However, under pressure, it will have different sequence of phase transitions than Hf: hcp→bcc instead of hcp→ω→bcc. An explanation is offered for this difference in terms of the competition between the band structure and the Ewald energy contributions.     

Induced Electronic and Thermal Effects of 86 MeV Nickel Ions in Bisphenol-A Polycarbonate

Bisphenol-A polycarbonate films were irradiated with 86 MeV swift heavy nickel ions at varying fluences, ranging from 1 × 10¹¹ to 1 × 10¹³ ions cm^?2, under vacuum at room temperature, to analyze the induced electrical and thermal modifications. AC conductivity measurements and UV-visible spectroscopy, Fourier transform infra-red (FTIR) spectroscopy, thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) techniques were applied to analyze the changes. A significant, exponential increase in conductivity at higher frequency was observed with the increase of nickel ion fluence. UV-visible analysis corroborated the results of the AC conductivity measurement, revealing the increase in size of the carbon clusters embedded in the polymer network, with the increase of heavy ion fluence. FTIR analysis revealed the formation of alkene and alkyne end groups at higher doses, which further supported the suggestion that the variation in electrical properties induced by the ion irradiation of the polymer was due to development of a carbonaceous phase inside the polymer due to the irradiation. Thermal analysis, i.e., TGA and DSC patterns, showed that chain-scission was the leading phenomena in the heavy ion-irradiated polycarbonate samples, resulting in degradation of their thermal stability.     

Magnesium ion transport in poly(ethylene oxide)-based polymer electrolyte containing plastic-crystalline succinonitrile

A new composition of magnesium (Mg)-ion-conducting polymer electrolyte comprising poly(ethylene oxide) (PEO) complexed with Mg trifluoromethanesulfonate (Mg triflate or Mg(Tf)₂) containing different amounts of a nonionic plastic crystal succinonitrile (SN) has been prepared and characterized. High polarity and rotational disorder of the SN molecules in the plastic-crystalline phase, supports the enhancement of ionic conductivity of the PEO-Mg(Tf)₂ complex system, showing a maximum room temperature ionic conductivity of ～6?×?10^-4 S cm^?1 observed with the addition of 50 wt.% of SN. X-ray diffraction, optical microscopy, and differential scanning calorimetry suggest a substantial structural modification, decrease in crystallinity, and various interactions in the polymer electrolyte components due to addition of SN. The cyclic voltammetry, impedance, and dc polarization studies confirm the Mg-ion conduction in the PEO complex. The electrochemical potential window of the electrolyte, observed from the linear sweep voltammetry, is determined to be ～4.1 V. The performance characteristics of the SN-incorporated polymer electrolyte system indicate their potential applicability as electrolytes in ionic devices including Mg batteries.     

A silicon-position dependent 6-endo-trig cyclization during Tsuji–Trost alkylation

Two silylated cyclohexenes products have been prepared by using a Tsuji–Trost palladium-catalyzed cyclization. It involves the generation of a cationic π-allylic palladium complex bearing a triethylsilyl group on C-3, which cyclizes via a 6-endo-trig process to afford the cyclohexene derivatives. It is also demonstrated that the position of the silyl group on the starting allylic substrate strongly influenced the reaction. It could favor either the production of the expected cyclohexenyl ring or a diene by an elimination that occurs on the silyl-substituted C-2 π-allylic palladium complex.     

A catalyst-free protocol for direct oxidative esterification of alcohols and aldehydes

A fast, simple, and efficient protocol for the direct conversion of alcohols and aldehydes to methyl ester has been developed using TsNBr₂ without any catalyst. The one pot reaction proceeds in the presence of a base at room temperature in methanol, to produce the corresponding methyl ester in high yield within a short time.     

A facile microwave assisted synthesis of spiro-1,3-oxazines from N-(2-(cyclohex-1-en-1-yl)ethyl)amides

A mild and efficient methodology has been developed for the synthesis of spiro-1,3-oxazine derivatives by the microwave assisted cyclization of N-2-(1′-cyclohexenyl)ethyl-acetamides/benzamides. The reaction was catalyzed by in situ generated trimethylsilyl iodide and featured by its very short reaction time. The starting materials were easily obtained by the condensation of substituted acetic/benzoic acids with 2-(1′-cyclohexenyl)ethyl amine.