Die Kristallstrukturen von KNdTe4, RbPrTe4 und RbNdTe4 — Untersuchungen zur thermischen Stabilität von KNdTe4 sowie Bemerkungen zu einigen anderen Vertretern der Zusammensetzung ALnTe4 (A = K,Rb, Cs und Ln = Seltenerd‐Metall)

Crystal Structures of KNdTe₄, RbPrTe₄, and RbNdTe₄ — Investigations concerning the Thermal Stability of KNdTe₄ as well as some Remarks concerning Additional Representatives of the Composition ALnTe₄ (A = K, Rb, Cs and Ln = Rare Earth Metal) Of the compounds ALnQ₄ (A = Na, K, Rb, Cs; Ln = Lanthanoid; Q = S, Se and Te) the crystal structures of the three new tellurides KNdTe₄, RbPrTe₄ and RbNdTe₄ were determined by X‐ray single‐crystal structure analysis and of the three additional new ones KCeTe₄, KPrTe₄ and CsNdTe₄ by X‐ray powder diffraction experiments. All six new compounds are isotypic with KCeSe₄. Characteristic for the crystal structure of the compounds mentioned above are layers built from (Q₂)^2— dumbbells in form of 4.3².4.3 nets with embedded cations A⁺ and Ln³⁺ between them, which are coordinated eightfold in form of square‐shaped antiprisms by Q ions. The distances Te‐Te within the dumbbells were found to be 277.8(2) pm for all investigated tellurides. By combination of X‐ray diffraction and DTA measurements it was shown that the compound KNdTe₄ is metastable at ambient temperature with a limited existence range between the temperatures 260 and 498 °C.     

GLOBAL ANALYSIS OF FLUORESCENCE DECAY: APPLICATIONS TO SOME UNUSUAL EXPERIMENTAL AND THEORETICAL STUDIES

The methodology for the simultaneous analysis of fluorescence decay curves is shown to create the possibility for some new types of fluorescence decay experiments. These new experiments include the use of the T-format in anisotropy experiments without the need to match the timing characteristics of photomultiplier tubes. Decay surfaces obtained at multiple timing calibrations can be analyzed simultaneously to resolve widely differing decay rates. Methodologies are described for the discrimination of associative from nonassociative behavior for multiexponential anisotropy decay. A systems theory approach to the analysis of excited state reactions is described.     

Diastereoselective hydroformylation of 2-substituted allylic o-DPPB-esters-on the origin of 1,2-asymmetric induction

2-Substituted secondary alcohol o-DPPB esters (o-DPPB=ortho-diphenylphosphanylbenzoyl) have been prepared and their o-DPPB-directed diastereoselective hydroformylation examined. It was found that the diastereoselectivity increased as a function of the steric demand of the substituents both at the stereogenic center and in the alkene 2-position. Hydrolytic cleavage of the o-DPPB group afforded-via the lactols 29-the corresponding lactones 30, the relative configurations of the vicinal stereogenic centers of which were ascertainable by 2D-NOESY spectroscopy. In addition, a crystal structure analysis of the hydroformylation product 2 d provided further confirmation of the relative configuration. Replacement of the ester carbonyl group of the o-DPPB by a methylene unit resulted in significantly worse diastereoselectivity in the course of the hydroformylation (34-->35), which indicates a decisive role for the ester carbonyl function. All the experimental observations were combined in a model of the origin of the 1,2-asymmetric induction during the title reaction. The key feature is the consideration of diastereomeric trigonal-bipyramidal rhodium-hydrido-olefin complexes I and II, capable on the basis of the Hammond postulate of acting as good models for the transition states of the selectivity-determining hydrometalation step. Investigation of these complexes by force-field methods indicated good correlation between theoretically predicted and experimentally determined diastereoselectivities.     

‘Non-Koopmans’ States in Stilbene Cations and a Remarkable Example to the «SDT-Equation»: Indeno [2,1-a]indene

The radical cations of indeno [2, 1-a]indene ( 1 ), stilbene ( 2 ) and 3, 5, 3', 5'-tetramethylstilbene ( 3 ) were prepared by γ-irradiation of the neutral precursors in an electron-scavenging matrix at 77 K . Their electronic spectra were recorded and compared to the photoelectron spectra ( PE .) of the neutral precursors. The results show that either the fourth or the fifth excited doublet state of the cations is of «Non-Koopmans» type, with specific doublet energy (D) D (²B_g)=2.74 eV ( 1 ⁺), =2.59 eV ( 2 ⁺), =2.49 eV ( 3 ⁺). Remarkably, 1 ⁺ possesses two electronic states in the 2.7-2.8 eV energy range: ²A_u («Koopmans»-type) and ²B_g («Non -Koopmans»-type). The «SDT»-equation \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm D} = \sqrt {{\rm S} \cdot {\rm T}} $\end{document} approximately connecting excited singlet (S) and triplet (T) states of a neutral alternant system with the excited doublet (D) states of its radical cation - provided e-promotion occurs For all three excited states between the same (paired) orbitals-is satisfyingly exemplified by 1 : S¹ = 3.92 eV and T¹= 2.06 eV for 1 , D^{4 or 5}=2.74 eV for 1 ⁺.     

CdSe and CdSe/CdS nanorod solids

We demonstrate the self-organization of CdSe nanorods into nematic, smectic, and crystalline solids. Layered colloidal crystals of CdSe nanorods grow by slow destabilization of a nanocrystal solution upon allowing the diffusion of a nonsolvent into the colloidal solution of nanocrystals. The colloidal crystals of nanorods show characteristic birefringence, which we assign to specific spherulite-like texture of each nanorod assembly. To demonstrate the general character of nanorod self-assembly technique, CdSe/CdS heterostructure nanorods were organized into highly luminescent superlattices.     

Microchip electrophoresis for chiral separations

Microchip electrophoresis (MCE) is a promising new technique for the separation of enantiomers. This recently introduced technique enables chiral separations to be performed in seconds on tiny micromachined devices. This review is intended to give a brief introduction into the principles of chiral separations with MCE with regard to methodology and instrumentation. Different approaches to realize chiral separations in microfluidic devices are described and discussed. This review gives an overview of original work done in this field with emphasis on approaches to improve detection and resolution in chiral MCE.     

Accurate calibration of TXRF using microdroplet samples

TXRF has been applied in combination with VPD to the analysis of trace impurities in the native oxide layer of Si wafer surfaces down to the range of 10(8) atoms. cm(-2). Proper quantification of VPD/TXRF data requires calibration with microdroplet standard reference wafers. The precision of calibration function has been evaluated and found to allow quantification at a high level of 3 sigma confidence with microdroplet standard reference.