Thermal behaviour of glazed ceramic bodies

Journal of Thermal Analysis and Calorimetry - Flower-shaped Ni-doped Fe3O4/SnS2 composite was synthesized by a one-pot solvothermal method, where nanosized Ni-doped Fe3O4 particles were dispersed...     

Intermediates of N-Heterocyclic Carbene (NHC) Dimerization Probed in the Gas Phase by Ion Mobility Mass Spectrometry: C−H⋅⋅⋅:C Hydrogen Bonding Versus Covalent Dimer Formation

N-Heterocyclic carbenes (NHCs, :C ) can interact with azolium salts ( C−H⁺ ) by either forming a hydrogen-bonded aggregate ( CHC⁺ ) or a covalent C−C bond ( CCH⁺ ). In this study, the intramolecular NHC–azolium salt interactions of aromatic imidazolin-2-ylidenes and saturated imidazolidin-2-ylidenes have been investigated in the gas phase by traveling wave ion mobility mass spectrometry (TW IMS) and DFT calculations. The TW IMS experiments provided evidence for the formation of these important intermediates in the gas phase, and they identified the predominant aggregation mode (hydrogen bond vs. covalent C−C) as a function of the nature of the interacting carbene–azolium pairs.     

Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]− Building Block Via Solid-State NMR Spectroscopy,Polarized Neutron Diffraction,and First-Principle Calculations

The local magnetic structure in the [Fe^III(Tp)(CN)₃]⁻ building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions.     

Green and sustainable chemistry in Latin America: Which type of research is going on? And for what?

Green (and sustainable?) frame around ‘Inverted America’ (adapted from Torres García, 1943, Museo Juan Manuel Blanes, Montevideo, CC BY 4.0).

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Investigation of stress-velocity LSFEMs for the incompressible Navier-Stokes equations

In this contribution three mixed least-squares finite element methods (LSFEMs) for the incompressible Navier-Stokes equations are investigated with respect to accuracy and efficiency. The well-known stress-velocity-pressure formulation is the basis for two further div-grad least-squares formulations in terms of stresses and velocities (SV). Advantage of the SV formulations is a system with a smaller matrix size due to a reduction of the degrees of freedom. The least-squares finite element formulations, which are investigated in this contribution, base on the incompressible stationary Navier-Stokes equations. The first formulation under consideration is the stress-velocity-pressure formulation according to [1]. Secondly, an extended stress-velocity formulation with an additional residual is derived based on the findings in [1] and [5]. The third formulation is a pressure reduced stress-velocity formulation based on a condensation scheme. Therefore, the pressure is interpolated discontinuously, and eliminated on the discrete level without the need for any matrix inverting. The modified lid-driven cavity boundary value problem, is investigated for the Reynolds number Re = 1000 for all three formulations. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Application of the Redox-Transmetalation Procedure to Access Divalent Lanthanide and Alkaline-Earth NHC Complexes**

Divalent lanthanide and alkaline-earth complexes supported by N-heterocyclic carbene (NHC) ligands have been accessed by redox-transmetalation between air-stable NHC-AgI complexes and the corresponding metals. By using the small ligand 1,3-dimethylimidazol-2-ylidene (IMe), two series of isostructural complexes were obtained: the tetra-NHC complexes [LnI₂(IMe)₄] (Ln=Eu and Sm) and the bis-NHC complexes [MI₂(IMe)₂(THF)₂] (M=Yb, Ca and Sr). In the former, distortions in the NHC coordination were found to originate from intermolecular repulsions in the solid state. Application of the redox-transmetalation strategy with the bulkier 1,3-dimesitylimidazol-2-ylidene (IMes) ligand yielded [SrI₂(IMes)(THF)₃], while using a similar procedure with Ca metal led to [CaI₂(THF)₄] and uncoordinated IMes. DFT calculations were performed to rationalise the selective formation of the bis-NHC adduct in [SrI₂(IMe)₂(THF)₂] and the tetra-NHC adduct in [SmI₂(IMe)₄]. Since the results in the gas phase point towards preferential formation of the tetra-NHC complexes for both metal centres, the differences between both arrangements are a result of solid-state effects such as slightly different packing forces.