Magneto-transport and ferromagnetic resonance studies of polycrystalline La0.6Pb0.4MnO3 thin films

To understand the nature of grain boundaries in polycrystalline materials, magneto-transport and ferromagnetic resonance measurement have been performed in polycrystalline La_0.6Pb_0.4MnO₃ (LPMO) thin films prepared by pulsed laser deposition. Films are found to undergo a semiconductor to metal transition at 230 K and re-enter into the semiconducting state below 130 K. Microwave absorption measurements carried out as function of applied field show two components of resonant absorption signal. First component is in accordance with ferromagnetic transition of grains at Curie temperature and the second component shows antiferromagnetic transition of grain boundaries at 160 K. An additional non-resonant absorption signal centered at zero field has also been observed that supports transition from conducting to insulating grain boundaries at ∼160 K. Further, temperature dependence of resistance in semiconducting state at low temperatures is in accordance with coulomb blockade model indicating insulating nature of AFM grain boundaries.     

Quinoline and 2-nitroimino-1, 3-diazacycloalkane hybrids: Design,synthesis and insecticidal activity

A library of new hybrid molecules comprising quinoline, 2-nitroimino-1, 3-diazacycloalkane motifs were designed and synthesized as plausible neonicotinoid analogues. These compounds were synthesized from 2-chloro/aryloxy-3-formyl quinolines and guanidine nitrate with the coupling of 2-chloro/aryloxy-3-(chloromethyl)quinolines, 2-nitroimino-1, 3-diazacycloalkanes under phase transfer catalysis (PTC) as crucial step. All the compounds were obtained in excellent yields (80–90%) and were characterized by ¹H, ¹³C NMR and mass spectrometry. The newly generated compounds were screened for insecticidal activity against aphids in safflower field and some of them displayed moderate activity.     

A Facile and Efficient Synthesis of 4‐Arylidene‐2‐phenyl‐5(4H)‐oxazolones and Their Antimicrobial Evaluation against Selected Human and Phytopathogens

A simple and convenient method has been developed for the synthesis of a series of 2‐(4‐substituted phenyl)‐4‐(substituted arylidene)‐1,3‐oxazol‐5‐ones ( 5a–j ) via reactions of hippuric acid with differently substituted aromatic aldehydes ( 4a–j ) in sodium acetate, potassium acetate, calcium acetate, and ammonium acetate, respectively, which were tested for their efficiency as catalysts in both conventional and microwave‐assisted synthetic methods in presence of 4 Å zeolites. The title compounds were evaluated for their antimicrobial properties against selected human pathogens (bacterial and fungal) and phytopathogens (fungal) and were compared with standard drugs. The results of the study are reported.     

Biocidal and catalytic efficiency of ruthenium(III) complexes with tridentate Schiff base ligands

The reaction of the Schiff bases (obtained by condensing isatin with o‐aminophenol/o‐aminothiophenol/o‐aminobenzoic acid) with [RuX₃(EPh₃)₃] (where X = Cl/Br; E = P/As) in benzene afforded new, air‐stable Ru(III) complexes of the general formula [Ru(L)X(EPh₃)₂] (L = dianion of tridentate Schiff bases). In all these reactions, the Schiff base ligand replaces one triphenylphosphine/triphenylarsine and two chlorides/bromides from the ruthenium precursors. The complexes were characterized by elemental analyses, spectral (FT–IR, UV–vis, ¹H and ¹³C NMR for the ligands, and EPR) and electrochemical studies. All the metal complexes exhibit characteristic LMCT absorption bands in the visible region. The catalytic reactivity proved these complexes to be efficient catalysts in the oxidation of alcohols and C? C coupling. All the complexes were screened for their biocidal efficiency against bacteria such as Staphylococcus epidermidis and Escherichia coli and fungi such as Botrytis cinerea and Aspergillus niger at 0.25, 0.50 and 1% concentrations. Copyright © 2010 John Wiley & Sons, Ltd.     

Catalytic and antimicrobial studies of binuclear ruthenium(III) complexes containing bis-β-diketones

A series of new binuclear Ru(III) complexes of the type {[RuX₃(EPh₃)]₂(bis- β-dk)} [X = Cl/Br; E = P/As bis- β-dk = bis(β-diketone)] have been prepared by reacting [RuCl₃(PPh₃)₃], [RuCl₃(AsPh₃)₃], [RuBr₃(PPh₃)₃], [RuBr₃(AsPh₃)₃] with bis(β-diketones) in a 2:1 molar ratio in benzene. These complexes have been characterized by physico-chemical and spectroscopic methods. The redox property of the complexes were studied by cyclic voltammetric technique. The complexes were found to be effective catalysts for the aryl–aryl coupling and oxidation of benzyl alcohol, cyclohexanol, propan-1-ol and 2-methylpropanol to benzaldehyde, cyclohexanone, propionaldehyde and 2-methylpropionaldehyde, respectively, using molecular oxygen as primary oxidant. All the complexes have been screened for their antibacterial and antifungal activities.     

Existence of a new emitting singlet state of proflavine: femtosecond dynamics of the excited state processes and quantum chemical studies in different solvents

Proflavine (3,6-diaminoacridine) shows fluorescence emission with lifetime, 4.6 ± 0.2 ns, in all the solvents irrespective of the solvent polarity. To understand this unusual photophysical property, investigations were carried out using steady state and time-resolved fluorescence spectroscopy in the pico- and femtosecond time domain. Molecular geometries in the ground and low-lying excited states of proflavine were examined by complete structural optimization using ab initio quantum chemical computations at HF/6-311++G** and CIS/6-311++G** levels. Time dependent density functional theory (TDDFT) calculations were performed to study the excitation energies in the low-lying excited states. The steady state absorption and emission spectral details of proflavine are found to be influenced by solvents. The femtosecond fluorescence decay of the proflavine in all the solvents follows triexponential function with two ultrafast decay components (τ(1) and τ(2)) in addition to the nanosecond component. The ultrafast decay component, τ(1), is attributed to the solvation dynamics of the particular solvent used. The second ultrafast decay component, τ(2), is found to vary from 50 to 215 ps depending upon the solvent. The amplitudes of the ultrafast decay components vary with the wavelength and show time dependent spectral shift in the emission maximum. The observation is interpreted that the time dependent spectral shift is not only due to solvation dynamics but also due to the existence of more than one emitting state of proflavine in the solvent used. Time resolved area normalized emission spectral (TRANES) analysis shows an isoemissive point, indicating the presence of two emitting states in homogeneous solution. Detailed femtosecond fluorescence decay analysis allows us to isolate the two independent emitting components of the close lying singlet states. The CIS and TDDFT calculations also support the existence of the close lying emitting states. The near constant lifetime observed for proflavine in different solvents is suggested to be due to the similar dipole moments of the ground and the evolved emitting singlet state of the dye from the Franck-Condon excited state.     

Fox-Flory constant K obtained by viscometric measurements for poly(ethyl methacrylate) and poly(methyl methacrylate) systems

Poly(ethyl methacrylate) and poly(methyl methacrylate) prepared by benzoyl peroxide-catalyzed polymerization were fractionated. The Fox-Flory constant K was determined for these polymers by viscometry in several good and bad solvents. Application of some empirical methods for evaluation of K are also briefly discussed in relation to our results.     

Photopolymerization initiated by charge transfer complex. II. Photopolymerization of methyl methacrylate with the use of γ-picoline–bromine charge transfer complex as photoinitiator

Polymerization of MMA was carried out in the presence of visible light (440 nm) with the use of γ-picoline-bromine charge transfer complex as the initiator. The rate of polymerization R_p increases with increasing monomer concentration and the monomer exponent was computed to be unity. The rate of polymerization increases with increasing initiator concentration. The initiator exponent was computed to be 0.5. The reaction was carried out at three different temperatures and the overall activation energy was calculated to be 4.5 kcal/mol. The polymerization was inhibited in the presence of hydroquinone. Kinetic and other evidence indicates that the overall polymerization takes place by a radical mechanism.     

Do penta- and decaphospha analogues of lithocene anion and beryllocene exist? Analysis of stability,structure, and bonding by hybrid density functional study

Stability in penta- and decaphospha analogues of lithocene anion and beryllocene is investigated by complete structural optimization at the B3LYP/6-31G level. Natural bond orbital analysis is carried out to examine the bonding between the metal and the ligands. The heterolytic dissociation energies of 667 and 608 kcal/mol predicted by B3LYP/6-311+G//B3LYP/6-31G calculations for CpBeP(5) and (P(5))(2)Be are comparable with the observed value of 635 +/- 15 kcal/mol in ferrocene. The high stability in CpBeP(5) and (P(5))(2)Be shows that these species are isolable under appropriate conditions. Lithocene anion and its phospha analogues possess lower stability toward dissociation into ionic fragments. A novel observation of the present study is that CpBeP(5) and (P(5))(2)Be have lowest energies when the two planar ligands are arranged perpendicular to each other such that one of the ligands, cyclo-P(5), is eta(1)-coordinated while the second ligand is eta(5)-coordinated to Be. The resulting structure having C(s)() point group (denoted as C(s)()(p)) is predicted to be 22 and 28 kcal/mol lower than the staggered sandwich geometry in CpBeP(5) and (P(5))(2)Be, respectively, at the B3LYP/6-311+G//B3LYP/6-31G level. In the analogous lithocene anions [CpLiP(5)](-) and [(P(5))(2)Li](-) also the C(s)()(p) structures are found to be the lowest energy structures, though their relative stabilities are small. We also characterized the geometry with both ligands eta(1)-coordinated to the metal in a linear arrangement having the D(2)(h)() point group in the decaphospha analogues [(P(5))(2)Li](-) and (P(5))(2)Be. This structure is found to be higher in energy than the C(s)()(p) structure. The D(2)(h)() structure could not be located as a potential minimum in the biscyclopentadienyl complexes and their pentaphospha analogues. Both the C(s)()(p) and D(2)(h)() structures are characterized for the first time in metallocenes. The D(2)(h)() structure seems to be a unique feature in the decaphospha metallocenes under consideration. Covalent bond formation between beryllium and phosphorus atom P(1) of eta(1)-(cyclo-P(5)) is more pronounced (bond orders 0.43-0.49) than that between Be and C(1) of eta(1)-Cp (bond orders 0.24-0.27). Though both eta(1)-coordinated cyclo-P(5) and Cp exhibit C(2)(v)() point groups, bond alternation is less pronounced in the former. The Wiberg P-P bond orders in the eta(1)-(cyclo-P(5)) of CpBeP(5) and (P(5))(2)Be having C(s)()(p) structures are in the range 1.29-1.47. These ring bond orders indicate that the P(5) ring retains aromaticity to a large extent in the eta(1)-mode of bonding with Be. Second-order perturbational energy analysis of the Fock matrix in the natural bond orbital basis reveals that there is a significant stabilizing interaction of approximately 123 kcal/mol between the lone pair orbital of P(1) and the 2s orbital of Be in the C(s)()(p) structures.