Novel D-A-π-A1 Type Organic Sensitizers from 4,7-Dibromobenzo[d][1,2,3]thiadiazole and Indoline Donors for Dye-Sensitized Solar Cells

Two novel D-A-π-A1 metal-free organic dyes of the KEA series containing benzo[d][1,2,3]thiadiazole (isoBT) internal acceptor, indoline donors fused with cyclopentane or cyclohexane rings (D), a thiophene as a π-spacer, and a cyanoacrylate as an anchor part were synthesized. Monoarylation of 4,7-dibromobenzo[d][1,2,3]thiadiazole by Suzuki-Miyamura cross-coupling reaction showed that in the case of indoline and carbazole donors, the reaction was non-selective, i.e., two monosubstituted derivatives were isolated in each case, whereas only one mono-isomer was formed with phenyl- and 2-thienylboronic acids. This was explained by the fact that heterocyclic indoline and carbazole fragments are much stronger donor groups compared to thiophene and benzene, as confirmed by cyclic voltammetry measurements and calculation of HOMO energies of indoline, carbazole, thiophene and benzene molecules. The structure of monoaryl(hetaryl) derivatives was strictly proven by NMR spectroscopy and X-ray diffraction. The optical and photovoltaic properties observed for the KEA dyes showed that these compounds are promising for the creation of solar cells. A comparison with symmetrical benzo[c][1,2,3]thiadiazole dyes WS-2 and MAX114 showed that the asymmetric nature of benzo[d][1,2,3]thiadiazole KEA dyes leads to a hypsochromic shift of the ICT band in comparison with the corresponding benzo[c][1,2,5]thiadiazole isomers. KEA dyes have a narrow HOMO-LUMO gap of 1.5–1.6 eV. Amongst these dyes, KEA321 recorded the best power efficiency (PCE), i.e., 5.17%, which is superior to the corresponding symmetrical benzo[c][1,2,3]thiadiazole dyes WS-2 and MAX114 (5.07 and 4.90%).     

Novel 2-alkoxy- and 2-alkylthio-substituted pyrimidines containing 2-(1-methyl-1H-pyrrol-2-yl)vinyl moieties: optical and electrochemical properties

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Crystal structure variations in the series SrLnCuS3 (Ln = La,Pr, Sm,Gd, Er and Lu)

The crystal structures of the complex sulfides SrLnCuS₃ (Ln = Sm, Gd, Er and Lu) have been determined and refined using powder X‐ray diffraction. The crystals are found to be orthorhombic, with the structure type changing consecutively in the order BaLaCuS₃ → Eu₂CuS₃ → KZrCuS₃ as the Ln³⁺ ionic radius decreases in the order La/Pr → Sm/Gd → Er/Lu. Variations of the structure parameters along the series of compounds studied are analyzed, and an effect caused by crystallochemical contraction on the stabilization of the respective structure types is demonstrated.     

Complexation of nickel (II) ion with B3 vitamin in aqueous dimethyl sulfoxide

The stability change of nickel(II) ion complexes including one and two nicotinamide (B₃ vitamin) molecules in aqueous dimethyl sulfoxide (X_DMSO = 0–0.85 m.f.) was studied at 298.2±0.1 K and 0.25 ionic strength value (NaClO₄) using the potentiometric method. The first stage constant of complexation increased until organic solvent concentration was 0.5 m.f. and reduced at higher DMSO content. The difference between complex and central ions solvation is a dominating contribution into the Gibbs energy change of mononicotinamide complex formation reaction. When the second ligand molecule was bonded into the coordination compound, the nicotinamide contribution to Δ_trG_r rose and became prevailing at X_DMSO = 0.7–0.85. The ligand was found to replace a water molecule in the coordination sphere of the cation according to spectrophotometric study results.      

Strain induced damage of ductile materials under compression

The problem of ductile damage and failure prediction at the upsetting of cylindrical specimens with artificial voids is solved by taking a change in stress triaxiality into account. It is shown that such a more accurate assessment leads to a greater shift of stress triaxialities into a range of negative values as compared to their averaged values. At such values of stress triaxiality the material can be subjected to compression without failure under arbitrarily large deformations due to healing of micro-defects. The constitutive equations of a recently developed tensorial framework for ductile damage [5] are applied to modelling. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the existence of a generalized solution of a nonlinear evolution system of equations in a domain unbounded in time

We consider a mixed problem with Dirichlet homogeneous boundary conditions and nonzero initial conditions for a nonlinear coupled evolution system of equations in a domain unbounded in time. The conditions of existence of a generalized solution are obtained. It is shown that no solution of the problem exists at a negative initial value of the energy integral.     

Polyaromatic-terminated iron(ii) clathrochelates as electrocatalysts for efficient hydrogen production in water electrolysis cells with polymer electrolyte membrane

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A tensorial framework for strain induced damage of plastically deformed metals

A tensorial framework for strain induced ductile damage of plastically deformed metals is developed in terms of both plastic flow theory and continuum damage mechanics. A symmetric second order damage rate tensor is used in order to study various processes with large finite deformations in combination with damage analysis. The definition of this tensor is physically meaningful since its volumetric and deviatoric parts describe the damage increments caused by an increase in the void volume and by a change in the shape of the void, respectively. Such a view on damage kinetics leads to the introduction of two measures for damage assessment which allow predicting not only a risk of macroscopic failure but also the onset of void coalescence. Material functions appearing in the constitutive equations for damage are determined both by own experiments and by known results from literature. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)