CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF A 4,4′-BIPY-BRIDGED BINUCLEAR ZINC(II) COMPLEX, 2[R2NCS2]2 · Zn(4,4′-BIPY) (R=PIPERIDYL)

Abstract

The crystal structure of the title complex 2[R₂NCS₂]₂ · Zn(4,4′-bipy) (R = Piperidyl), 1, revealed that it consists of dimers made up from two crystallographically independent molecules. Each zinc atom in 1 forms a 5-coordinate pseudo-square-based pyramidal arrangement (with four Zn-S and one Zn-N interactions). Bondlengths to Zn with the coordinating atoms are comparable to those in other Zn(II) dithiocarbamate complexes. The piperidine ring has a chair conformation. To allow improved packing, the title complex molecules form an approximately linear arrangement extending along both a and b. TGA showed that 1 is decomposed in two close steps to produce ZnS as identified by residual weight. The complex 1 crystallizes in the monoclinic space group C2/c with cell parameters: a = 22.021(5), b = 22.215(3), c = 17.537(2) Å, β = 93.49(2)°, V = 8563(3) ų and Z = 8. The structure was refined by full-matrix least-squares methods to R = 0.067, R_w = 0.114.     

A dinuclear diamagnetic copper(II) complex [Cu2(ophen)2]Cl2 with hydroxylated phen

A dinuclear diamagnetic copper(II) complex, [Cu₂(ophen)₂]Cl₂ (Hophen = 2-hydroxy-1,10-phenanthroline), has been synthesized and characterized, providing good structural evidence for the long-debated Gillard mechanism.     

Synthesis,structure, spectral and magnetic properties of 4-methoxy- and 3-methylsalicylatocopper(II) complexes with 2-pyridylmethanol

The synthesis and characterization of [Cu(4-MeOsal)₂(2-pyme)₂] (1) and [Cu(3-Mesal)₂(2-pyme)₂] (2) (where 4-MeOsal?=?4-methoxysalicylate, 3-Mesal?=?3-methylsalicylate and 2-pyme?=?2-pyridylmethanol) are reported. The composition and stereochemistry as well as the mode of coordination have been determined by elemental analysis, IR, electronic and EPR spectra as well as magnetization measurements over the temperature range 1.8–300?K. The crystal structures of Cu(4-MeOsal)₂(2-pyme)₂ and Cu(3-Mesal)₂(2-pyme)₂ have been determined.     

An Investigation into the Migration of Segments in Crosslinked Fluorinated Polyimide Adhesive

Crosslinked fluorinated polyimides (CFPI) were successfully synthesized to study and explore the effect of cross-linkage on the migration of fluorinated segments and on the adhesion strength. Characterization by dynamic thermomechanical analysis (DMA) and thermo gravimetric analysis (TGA) confirmed good thermal properties of CFPI. X-ray photoelectron spectroscopy (XPS) results showed that the ratio of fluorinated component (6FDA-ODA) concentration of the surface to the bulk decreased with the crosslink density. The water contact angle of CFPI was lower than that of non-crosslinked fluorinated polyimide, indicating that the migration of fluorinated groups to the surface was reduced by the presence of cross-linkage. Therefore, CFPI, with no fluorine segregation on the surface, exhibited excellent wetting of adherent surfaces and adhesion strength, which was proved by lap shear strength (LSS) measurements and scanning electron microscopy.     

A theory of flux peaking effect in channeling

The redistribution of the channeled ion flux in the transverse plane has been examined. General formulae describing the flux peaking effect are obtained. Main factors on which the effect depends are investigated. An analysis is made of back-scattering experiments. The study has been made for the axial and planar channeling.     

Charge carrier mobility,photovoltaic, and electroluminescent properties of anthracene‐based conjugated polymers bearing randomly distributed side chains

This article reports on the synthesis, characterization, and properties of various anthracene‐containing poly (p‐phenylene‐ethynylene)‐alt‐poly(p‐phenylene‐vinylene) (PPE‐PPV) polymers (AnE‐PVs) bearing statistical distributions of various side chains. Primarily, the ratio of linear octyloxy and branched 2‐ethylhexyloxy side chains at the poly(p‐phenylene vinylene) (PPV) parts was varied, leading to the polymers stat, stat1, and stat2. Furthermore, polymers also containing asymmetric substituted PPV and poly(p‐phenylene ethynylene) units (bearing methoxy and 2‐ethylhexyloxy side chains) were prepared yielding stat3, stat4, and stat5. These materials exhibit a broad variation in their photovoltaic properties. It is once more shown that side chains and their distribution can crucially affect the photovoltaic device performance. The introduction of units with asymmetric substitution into these systems seems to be harmful for their utilization in photovoltaic applications. Organic field‐effect transistors were fabricated to investigate hole mobilities in these new materials. Large variance was observed, falling in the range of almost two orders of magnitude, indicating rather different π–π stacking behavior of the polymer backbones owing to side‐chain modifications. Moreover, a selection of the new polymeric systems was investigated regarding their potential for light‐emitting diode (LED) applications. Polymer LEDs using the polymers AnE‐PVstat, ‐stat3, ‐stat4, and ‐stat5, as the active layer showed turn‐on voltage of ～2 V and exhibited red light emission. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Improving charge transport in poly(3‐hexylthiophene) transistors via blending with an alkyl‐substituted phenylene–thiophene–thiophene–phenylene molecule

A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Influence of the mode of deformation on recrystallisation kinetics in Nickel through experiments,theory and phase field model

Abstract

In this paper, we report the influence of the mode of deformation on recrystallisation kinetics through experiments, theory and a phase field model. Ni samples of 99.6% purity are subjected to torsion and rolling at two equivalent plastic strains and the recrystallisation kinetics and microstructure are compared experimentally. Due to significant differences in the distributions of the nuclei and stored energy for the same equivalent strain, large differences are observed in the recrystallisation kinetics of rolled and torsion-tested samples. Next, a multi-phase field model is developed in order to understand and predict the kinetics and microstructural evolution. The coarse-grained free energy parameters of the phase field model are taken to be a function of the stored energy. In order to account for the observed differences in recrystallisation kinetics, the phase field mobility parameter is a required constitutive input. The mobility is calculated by developing a mean field model of the recrystallisation process assuming that the strain free nuclei grow in a uniform stored energy field. The activation energy calculated from the mobilities obtained from the mean field calculation compares very well with the activation energy obtained from the kinetics of recrystallisation. The recrystallisation kinetics and microstructure as characterised by grain size distribution obtained from the phase field simulations match the experimental results to good accord. The novel combination of experiments, phase field simulations and mean field model facilitates a quantitative prediction of the microstructural evolution and kinetics.     

New insights into water‐soluble and water‐coordinated copper 15‐metallacrown‐5 gadolinium complexes designed for high‐field magnetic resonance imaging applications

The development of contrast agents specifically designed for high‐field magnetic resonance imaging (MRI) is required because the relaxation efficiency of classic Gd(III) contrast agents significantly decreases with increasing magnetic field strengths. With an idea of exploring the unique structure of lanthanide (Ln) 15‐MC‐5 metallacrowns, we developed a series of water‐soluble Gd(III) aqua‐complexes, bearing aminohydroxamate (glycine, α‐alanine, α‐phenylalanine and α‐tyrosine) ligands, with increasing number of water molecules directly coordinated to the Gd(III) ion: Gd(H₂O)₄[15‐MC_Cu(II)Glyha‐5](Cl)₃ ( 1 (Gd)), Gd(H₂O)₄[15‐MC_Cu(II)Alaha‐5](Cl)₃ ( 2 (Gd)), Gd(H₂O)₃[15‐MC_{Cu(II)Phalaha}‐5](Cl)₃ ( 3 (Gd)) and Gd(H₂O)₃[15‐MC_Cu(II)Tyrha‐5](Cl)₃ ( 4 (Gd)). In these systems, the Ln(III) central ion is coordinated by five oxygen donor atoms of the ligands and three or four inner‐sphere water molecules. The X‐ray crystal structure of metallacrown Ln(H₂O)_3,4[15‐MC_Cu(II)Rha‐5]³⁺ agrees with density functional theory predictions. The calculations demonstrate that the exchange of coordinated water molecules can proceed easily, resulting in increased relaxivity parameters. The longitudinal relaxivities (r₁) of 1 (Gd)– 4 (Gd) in water at ultrahigh magnetic field of 9.4 T were determined to be 11.5, 14.8, 13.9 and 12.2 mM^?1 s^?1, respectively. The ability to increase the number of Ln(III) inner‐sphere water molecules up to four, the planar metallacrown structure and the rich hydration shell due to strong hydrogen bonds between the [15‐MC‐5] moiety and bulk water molecules provide new opportunities for potential MRI applications.     

Simulating Dirac fermions with Abelian and non-Abelian gauge fields in optical lattices

In this work we present an optical lattice setup to realize a full Dirac Hamiltonian in 2+1 dimensions. We show how all possible external potentials coupled to the Dirac field can arise from perturbations of the existing couplings of the honeycomb lattice pattern. This greatly simplifies the proposed implementations, requiring only spatial modulations of the intensity of the laser beams to induce complex non-Abelian potentials. We finally suggest several experiments to observe the properties of the quantum field theory in the setup.