Intergranular magnetoresistance in Sr2FeMoO6 from a magnetic tunnel barrier mechanism across grain boundaries

We present magnetization (M) and magnetoresistance (MR) data for a series of Sr2FeMoO6 samples with independent control on antisite defect and grain-boundary densities, which reveal several unexpected features, including a novel switching-like behavior of MR with M. These, in conjunction with model calculations, establish that the MR in Sr2FeMoO6 is dominantly controlled by a new mechanism, derived from the magnetic polarization of grain-boundary regions acting like spin valves, leading to behavior qualitatively different from that usually encountered in tunneling MR. We show that a simple and useful experimental signature for the presence of this spin-valve-type MR (SVMR) is a wider hysteresis in MR compared to that in M.     

Design and synthesis of boron containing 2,4-disubstituted-phthalazin-1(2H)-one and 3,7-disubstituted-2H-benzo[b][1,4] oxazine derivatives as potential HGF-mimetic agents

We synthesized boron containing 2-(4-methoxybenzyl)-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioaborolan-2-yl)phenyl) phthalazin-1(2H)-one 3 and 7-methyl-3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-2H-benzo[b][1,4] oxazine 8. The reaction of compound 2 with B₂pin₂ using potassium acetate as the base and Pd(PPh₃)₂Cl₂ as the catalyst, produced the corresponding boron-containing derivative 3 as a white solid in 65% yield. Alternatively, we have synthesized compound 8 as a yellow solid in 59% yield using the Miyaura borylation reaction. The potassium trifluoro(4-(-methyl-2H-benzo[b][1,4]oxazine-3-yl)phenylborate 9 was then obtained after treatment of 8 with aqueous solution of KF₂H in methanol as white solid product in 60% yield. The biological activities of the synthetic compounds are currently being evaluated.     

Discrete macromolecular constructs via the Diels–Alder “Click” reaction

Functional polymeric materials with desired properties can be designed by precise control of macromolecular architectures. Over the recent years, click reactions have enabled efficient synthesis of a variety of polymers with different topologies via efficient polymer–polymer conjugations. While the copper catalyzed Huisgen type (3+2) dipolar cycloaddition between azide and alkyne has been widely used toward this goal, the Diels–Alder (DA) reaction offers an alternative click reaction that allow efficient macromolecular conjugations, oftentimes without the need of any additional reagent or catalyst. This article highlights, with illustrative examples, the power of the DA “click” reaction to efficiently synthesize a variety of different well‐defined macromolecular constructs in a modular fashion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Origins of the diastereoselectivity in hydrogen bonding directed Diels-Alder reactions of chiral dienes with achiral dienophiles: a computational study

In this study, the origins of diastereoselectivity in the hydrogen bonding assisted Diels-Alder reactions of chiral dienes with achiral dienophiles have been investigated with density functional methods. The distortion/interaction model has been applied to shed light on the origins of selectivity. C9-Substituted chiral anthracene templates (R = (CH(3))(OCH(3))(H), R = (CH(3))(OH)(H), R = (CH(3))(CH(2)CH(3))(H) and R = (-CH(2)-C(CH(3))(OCH(3))(H)) are used to rationalize the role of a stereogenic center and H-bonding on the product distribution ratio. Even though hydrogen bonding increases the reactivity of the diene, the stereoselectivity is reduced because of the hydrogen bonding capacity of both diastereomeric transition states. The interaction energies of the studied anthracene templates with N-methyl maleimide at the transition state correlate linearly with an increase in reactivity. The selectivity is determined by both favorable distortion and interaction energies. The π-facial selectivity induced by the presence of a chiral auxiliary in 1-substituted 1,3-pentadienes (R1 = (CH(3))(OCH(3))(H) and R1 = (CH(3))(OH)(H)) has also been modeled in order to rationalize the role of the stereogenic center and H-bonding on the stereoselectivity of an aliphatic diene. In both parts, the product distribution ratios calculated from Boltzmann distributions based on Gibbs free energies are in reasonable agreement with the experimental results. Finally the role of OH-substituted five-membered pyrrolidine on C9 of anthracene is investigated since the successful usage of the conformationally rigid pyrrolidines in asymmetric synthesis is well known. Overall, both in the acyclic system and in anthracene, the facilitation due to H-bonding is reflected in the interaction energies: the higher the difference in interaction energies in the transition structures of the two diastereomers, the more selective the H-bonding assisted Diels-Alder reaction is.     

Synthesis and complexes of an N4 Schiff-base macrocycle derived from 2,2'-iminobisbenzaldehyde

An N(4) tetradentate [1 + 1] Schiff base metal free macrocycle HL was prepared, by 1?:?1 condensation of 2,2'-iminobisbenzaldehyde (1) and diethylenetriamine, and characterised. Seven mononuclear complexes, [Zn(II)L(py)](BF(4)) (2), [Cu(II)L](BF(4))]·H(2)O (3), [Ni(II)L](BF(4))·H(2)O (4), [Co(II)L](BF(4))]·H(2)O (5), Fe(III)L(BF(4))(2)·2H(2)O·MeCN (6), [Co(III)L(NCS)(2)]·0.3py (7) and [Fe(III)L(NCS)(2)] (8), of L(-) are reported. The Cu(II) and Ni(II) complexes were prepared by a template approach whereas the others were accessed by metallation of pre-formed HL. The X-ray crystal structure determinations show that [Cu(II)L](BF(4)) and [Ni(II)L](BF(4)) feature square planar N(4) coordinated Cu(II) and Ni(II) centres, respectively, whereas [Fe(III)L(NCS)(2)]·NO(2)Me features an octahedral N(6) coordinated Fe(III) centre (two NCS anions bound axially) and the Zn(II) complex, which crystallised as 2{[Zn(II)L(py)](BF(4))}·py, features square pyramidal Zn(II) ions (a pyridine molecule bound axially). In all cases the N(4) macrocycle is bound equatorially to the metal ion. Cyclic voltammograms of the soluble BF(4) complexes, 2-5, were carried out in MeCN vs. 0.01 mol L(-1) AgNO(3)/Ag and revealed multiple, mostly irreversible or quasi-reversible, redox processes. The Zn(II) complex 2 exhibited two irreversible oxidation processes and one irreversible reduction process, all of which are ligand-centered. The Ni(II) complex 4 showed a process with a weak return wave at E(m) = +0.57 V (ΔE = 0.05 V). Interestingly, after controlled potential coulometry experiments on 2, 3 and 4 (at +0.48, +0.61 and +0.71 V which transferred 1.2, 1.0 and 1.6 e(-) equiv. per complex, respectively), a new reversible or quasi-reversible process was obtained, with a lower potential than beforehand (E(m) (ΔE)/V = +0.16 (0.08), +0.31 (0.13) and +0.45 (0.11) respectively).     

Nonlinear travelling waves in φ6 polarizable model

We present a complete theoretical analysis of the periodic and non-periodic travelling waves in a diatomic chain model, in the continuum limit by incorporating nonlinear sixth order polarization potential (φ⁶) at the anion site. We have formulated a nonlinear lattice dynamical theory in which various energy curves are obtained for different types and magnitudes of the core-shell force constants. For periodic solutions, we have obtained two types of commensurate wave amplitudes which propagate in the opposite direction with respect to each other. For nonperiodic solutions, we have obtained various travelling excitations such as kink, antikink, excitons etc. for different values of the mass ratio and velocity parameter. The dipole moment per unit charge for SrTiO₃ has been calculated and it is found that the nonlinear excitations in this model carry large amount of energy as compared to those obtained from harmonic and anharmonic optical phonons in the φ⁴-polarizable model.     

Phonon dispersion in quasiperiodic semiconductor superlattices

The phonon spectra of unstrained and strained quasiperiodic semiconductor superlattices (QSSL) have been calculated using one-dimensional linear chain model. We consider two types of quasiperiodic systems, namely cantor triadic bar (CTB) and Fibonacci sequences (FS), constituting of AlAs, GaAs and GaSb of which the latter two have a lattice mismatch of about 7%. The calculations have been made using transfer matrix method and also with and without the inclusion of strain. We present the results on phonon spectra of two component CTB and two as well as three component FS semiconductor superlattices (SSL), thickness and order dependence on LO mode of GaAs, effect of strain on LO frequency of GaAs. The calculated results show that the strain generated due to lattice mismatch reduces significantly the magnitudes of the confined optical phonon frequency of GaAs.     

Effect of strain on vibrational modes in strained layer superlattices

We have investigated the lattice vibrational properties of a two-component strained layer semiconductor superlattice (GaAs) _n1 (GaSb) _n2 using a one-dimensional linear chain model and transfer matrix method [1]. Effect of strain, arising due to the lattice mismatch (∼ 7%) has been considered explicitly in the equation of motion. We show for the first time that the optical vibrational frequency increases (in the case of (GaAs)₄ (GaSb) _n ) or decreases (in the case of (GaAs) _n (GaSb)₄) with increase of layer thicknessn, in either type of superlattices. Raman scattering measurements on some other similar systems support our findings.     

Phonons and periodons in IV–VI semiconductor superlattices

We have calculated the phonon and periodon dispersion relations in IV–VI semi-conducting bulk PbTe and SnTe and their superlattice structure. The model used here is a one-dimensional lattice which includes harmonic interactions up to second neighbours as well as on-site nonlinear electron-ion interactions at the anion site. We calculate the phonon and periodon dispersion relations in bulk and PbTe-SnTe superlattice for the transverse optic and acoustic modes using the transfer matrix method. Our analysis has predicted correct nature of the folding of acoustic and confinement of optical phonons at various frequency intervals corresponding to pass and stop bands of the superlattices.     

Anharmonic oxygen vibration and mode softening in Tl2Ba2Ca2Cu3O10 superconductor

The softening of the IR active 300 cm⁻¹ phonon mode in Tl-2223 superconductor, aroundT _c has been explained by considering a sixth order polarization potential at the off-center oxygen ion site in the Tl-O plane, and by using a nonlinear lattice dynamical theory. The present theory explains, more or less satisfactorily, the unusual temperature dependence of oxygen ion vibration and frequency shifts at higher temperature. The existence of strong nonlinear electron-phonon interaction atT _c has been emphasized.