Cyclische Kieselsäurederivate

Cyclic Silicic Acid Derivatives By reaction of SiCl₄ with oxygen at elevated temperatures a number of chlorsiloxanes consisting of more or less fused rings can be prepared of which those components of low molecular weight can be separated by combining distillation and crystallization. Methyl and ethyl esters of silicic acids are obtained by reaction with methyl or ethyl nitrite, resp. The compounds are characterized by silicon n.m.r. and mass spectroscopy.     

Thermokinetic analysis of two-step curing reactions in melt: Part I. Investigation of low molecular model systems

Kinetic investigations of thermo-controlled two-step reactions between an uretdione cross-linker and OH-groups are undertaken. Non-isothermal DSC measurements are chosen for the determination of the kinetic parameters (E, A, n) using of THERMOKINETICS software. The system can be described very accurately with a four-step kinetic model of consecutive reactions. On the basis of the kinetic model and parameters the realization of the first reaction step, which is the formation of the allophanate network is simulated. Finally, the result of the calculated progress of the reaction is evaluated by FT-IR and isothermal DSC measurements.     

Dediazoniation of Arenediazonium Ions in Homogeneous Solution. Part IX. Spectral Evidence for a Homolytic Mechanism Involving Pyridine Complexes

The mechanism of dediazoniation of arenediazonium tetrafluoroborates in 2,2,2-trifluoroethanol (TFE) is strongly dependent on the concentration of added pyridine. The added base complexes with the diazonium ion and diverts it to a homolytic pathway. Complex formation is indicated by the disappearance of the \documentclass{article}\pagestyle{empty}\begin{document}$\raise1pt\hbox{---} \mathop {\rm N}\limits^ \oplus \equiv {\rm N}\raise1pt\hbox{---}$\end{document} stretching vibration and appearance of a new band at about 1640–1690 cm^?1 ascribed to the \documentclass{article}\pagestyle{empty}\begin{document}$\raise1pt\hbox{---} {\rm N}\raise1pt\hbox{=\kern-3.45pt=} {\rm N}\raise1pt\hbox{---} \mathop {\rm N}\limits^ \oplus {\rm C}_5 {\rm H}_5$\end{document} system. UV. and NMR. results support this conclusion. Chemically induced dynamic nuclear polarization (CIDNP) experiments clearly implicate a radical-pair as an important intermediate in the decomposition of these complexes.     

The detection of oxygen in magneto-optical layers with SIMS

The detection of oxygen in magneto-optical layers is of fundamental importance for the characterization of the stability of RE-TM material. The magnetic properties are directly influenced by oxide formation. Oxygen depth profiles are carried out by using the SIMS technique. A comparison with magnetic measurements showed a clear conformity. We were able to study the oxidation behaviour of various layers at room temperature and at higher values up to 250° C for several hours. It could be shown that aluminum is a successful material for the protection of RE-films against oxidation. The difficulties of translating SIMS counting rates into concentration values were overcome by using EPMA. Specially prepared reference samples were measured by this technique and could then be used as standard samples for SIMS.     

Darstellung und Eigenschaften von π-Cyclopentadienylrhodium-bis(tert.-phosphit)-Komplexen

The half-sandwich type compounds C₅H₅Rh[P(OR)₃]₂ (R = CH₃, C₂H₅, C₆H₅, p-CH₃C₆H₄, p-ClC₆H₄) have been prepared from [(P(OR)₃)₂RhCl]₂ and NaC₅H₅. The NMR. data as well as the IR. and mass spectra of the new compounds will be discussed. The preparation of C₅H₅Rh(CO)P(OC₂H₅)₃ is also reported.     

A stable binuclear complex containing PdHPd bonds

The preparations of the binuclear hydrido-bridged cations [(terdentate ligand)Pd(μ-H)Pd(terdentate ligand)]⁺ from [(terdentate ligand)Pd(acetone)]⁺ and NaO₂CH and [(terdentate ligand)Pd(μ-H)Pt(terdentate ligand)]⁺ from [(terdentate ligand)Pd(acetone)]⁺ and [(terdentate ligand)PtH] (terdentate ligand = 2,6-(Ph₂PCH₂)₂C₆H₃) are reported. The preparation of the cation [(terdentate ligand)Pt(μ-H)Pt(terdentate ligand)]⁺ is also reported.     

Particle sizing by time-resolved Mie calculations—A numerical study

If a small transparent particle is illuminated with a short laser pulse, the signals of the individual scattering light orders appear temporally successively. Since to each scattered light order belongs a specific optical path through the particle, the particle size can be determined from the time difference between the detected scattered light signals. For the case of a detector position within the backscatter region, which especially is important in measuring practice, the time difference between the specular reflection signal and the signal after a single internal reflection (refraction of second order) must to be evaluated. In the numerical simulation we generate the concerned scattered light signals by using time-resolved Mie calculations and in this paper we present the geometrical models, which permit a correct interpretation of the temporal behavior of these pulse-induced scattered light signals.     

Assemblies from metallic and semiconducting nanocrystals

Optical properties of nanomaterials such as semiconductor and metal quantum dots are important for sensors and photovoltaic applications. We report on optical, microscopic, and AFM investigations on bulk and single nanoobjects such as metal and semiconducting nanoparticles. Firstly, of special interest is the investigation of Ag metal nanoaggregates formed in zeolites. Here, the defined structure of the zeolite serves both as size directing and a stabilizing agent. The size selected Ag aggregates fluoresce in the zeolite cages even after storage under ambient conditions for almost one year. In addition, single Ag particles escape the cages and can be investigated by fluorescence microscopy also with respect to sensor applications. Secondly, with respect to photovoltaic applications, energy transfer among organic dye molecules and semiconductor quantum dots is of great importance. We report on the extension of the optical absorption of ZnSe quantum dots into the UV regime and investigate excitation energy transfer within self-assembled nanoaggregates of surface functionalized QDs and fluorescent styrylpyridine dyes.