Emission,Emissionslebensdauer und Absorption von [Cr urea6]X3-Einkristallen

Emission and absorption polarization spectra as well as emission lifetimes between room temperature and 5 °K have been measured of [Cr urea₆]X₃ single crystals, where X stands for ClO ₄ ^– , J^–, NO ₃ ^– , Br^–, Cl^–, F^–, and X₃ for JSO ₄ ^3– . The strong temperature dependence of the fluorescence/phosphorescence-ratios, and of the emission lifetimes is discussed. The differences between the spectra as well as the emission lifetimes of the various salts can be attributed to an anion dependent trigonal perturbation.

Die Autoren danken dem Verband der Chemischen Industrie für finanzielle Unterstützung dieser Arbeit.     

Encapsulation of Functional Organic Compounds in Nanoglass for Optically Anisotropic Coatings

A novel approach is presented for the encapsulation of organic functional molecules between two sheets of 1 nm thin silicate layers, which like glass are transparent and chemically stable. An ordered heterostructure with organic interlayers strictly alternating with osmotically swelling sodium interlayers can be spontaneously delaminated into double stacks with the organic interlayers sandwiched between two silicate layers. The double stacks show high aspect ratios of >1000 (typical lateral extension 5000 nm, thickness 4.5 nm). This newly developed technique can be used to mask hydrophobic functional molecules and render them completely dispersible in water. The combination of the structural anisotropy of the silicate layers and a preferred orientation of molecules confined in the interlayer space allows polymer nanocomposite films to be cast with a well‐defined orientation of the encapsulated molecules, thus rendering the optical properties of the nanocoatings anisotropic.     

A finite-element approach in stream-tube method for solving fluid and solid mechanics problems

This paper presents a theoretical formulation in which the stream-tube method (STM) is examined through a variational approach for solving solid strain and fluid flow problems with finite elements. The analysis considers a reference domain, used as computational domain, related to the physical domain by an unknown transformation function to be determined numerically. Mass conservation is automatically verified by STM. The variational approach leads to eliminate the pressure in fluid problems and avoids to set up a mixed displacement–pressure procedure in the case of incompressible solids. Examples are given for fluid flows, applications and comparisons are also provided in the bending problem in elasticity.     

The reaction of hexamethyl phosphoric triamide (HMPT) with phosphoryl chloride : A reexamination. Application to a novel preparation of BOP reagent for peptide coupling

The reaction of hexamethyl phosphoric triamide with phosphoryl chloride at R.T. gave actually a chlorophosphonium salt. This reaction is illustrated in a novel preparation of BOP reagent for peptide coupling in good conditions.     

Numerical simulation of complex flows of non-Newtonian fluids using the stream tube method and memory integral constitutive equations

In this paper a memory integral viscoelastic equation is considered for simulating complex flows of non-Newtonian fluids by stream tube analysis. A formalism is developed to take into account co-deformational memory equations in a mapped computational domain where the transformed streamlines are parallel and straight. The particle-tracking problem is avoided. Evolution in time and related kinematic quantities involved with a K-BKZ integral constitutive model are easily taken into account in evaluating the stresses. Successive subdomains, the stream tubes, may be considered for computing the main flow in abrupt axisymmetric contractions from the wall to the central flow region. The ‘peripheral stream tube’ close to the duct wall is determined by developing a non-conventional modified Hermite element. A mixed formulation is adopted and the relevant non-linear equations are solved numerically by the Levenberg-Marquardt algorithm. Although the singularity at the section of contraction is not involved explicitly, the results obtained for the peripheral stream tube clearly show the singularity effects and the extent of the recirculating zone near the salient corner. The algorithm is stable even at high flow rates and provides satisfactory solutions when compared with similar calculations in the literature.     

Vibrational Spectra of Anhydrous Lanthanum,Europium, Gadolinium,and Dysprosium Nitrates and Oxinitrates

IR. and Raman spectra of LnONO₃ (50–4,000 cm^?1, Ln?La, Gd, Eu, and Dy) are reported and discussed. The low frequency region of the spectra reflects the cubic structure of these compounds. The dimensions of the cubic unit cells determined by X-Ray powder diagrams are: 12.81 ± 0.05 Å for EuONO₃, 12.69 ± 0.05 Å for GdONO₃, and 12.67 ± 0.05 Å for DyONO₃. The vibrational frequencies of the nitrato group are consistent with a bidentate nitrate of C_2v symmetry. The synthesis of anhydrous Ln (NO₃)₃ (Ln?La, Gd, Eu, and Dy) by dehydration of the corresponding penta- or hexahydrates is described. The IR. and Raman spectra (50-4,000 cm^?1) are analysed. Splitting of the bands point to a complex structure of these compounds. All six vibrational modes of the nitrato group are observed and the data are again consistent with bidentate NO^?₃ moieties. Finally, an analytical control of the purity of Ln (NO₃)₃ is suggested.     

Structure and spectroscopy of Tb[Au(CN)2]3.3H2O

The compound Tb[Au(CN)2]3.3H(2)O crystallizes in a layered structure in the hexagonal space group P6(3)/mcm with the 9-coordinate environment of Tb3+ comprising six (CN)- and three OH2 in a tricapped trigonal prism. The shortest Au...Au distance is 3.31 angstroms. The vibrational spectra show that the series Ln[Au(CN)2]3.3H2O (Ln = Y, Pr, Sm, Eu, Tb) are isostructural. The electronic spectra of Eu[Au(CN)2]3.3H2O clearly show that Eu3+ occupies one site of spectroscopic site symmetry D3h, in agreement with the crystallographic data. The electronic emission and absorption spectra of Tb[Au(CN)2]3.3H2O have been recorded at temperatures down to 1.5 K, and the f-f pure electronic transitions are interpreted in detail as arising from the lowest electronic states (in D3h symmetry) (7F6)E' in absorption and (5D4)E' in emission. At low energy, further bands are assigned to the vibronic structure of the CN stretching and water stretching modes, with the latter more predominant. Although the CN stretching vibrations show exclusive infrared or Raman activity in Tb[Au(CN)2]3.3H2O, both of these infrared and Raman active modes are observed in the two-center vibronic transitions. The reasons for this are discussed.     

Etude par rmn de31p de la reaction de l'hexamethylphosphotriamide avec le trichlorure de phosphoryle

The reaction of HMPT with POCl₃ was studied by ³¹P NMR at various temperatures and stoechiometries. Progressive substitution of chlorine atoms of phosphoryl chloride by HMPT molecules was observed. Six new species were involved in the system. The main produce was the $\text{1}\text{1}$ adduct, (Me₂N)₃P⁺Cl, O₂PCl₂^?, analogous to Vilsmeier complex.