Quantenchemische Untersuchungen zur Molekül- und Elektronenstruktur einfacher Azomethinimine und verwandter Verbindungen

Quantum Chemical Investigations of the Molecular and Electronic Structure of Simple Azomethine Imines and Related Compounds The molecular and electronic structure of simple azomethinimines are investigated by means of MINDO/3 and CNDO/2 calculations. The calculated molecular geometry is compared with X-ray results obtained for these compounds. Except for the NN-bond lengths MINDO/3 satisfactorily describes the molecular structure of azomethinimine and related π-electronic systems. The charges at the atoms along the conjugated chain are alternating as in polymethines. The terminal carbon atom carries a negative charge. This charge brings about an appreciable shielding of this carbon atom such as found in the ¹³C-n.m.r. spectrum. This result does not contradict a stabilization of azomethinimines in the crystal via = CH…︁OC interactions.     

Synthesis and Reactivity of Iron(II) Complexes with a New Tripodal Imine Ligand

A new tripodal imine ligand tris(2-(propan-2-ylideneamino)ethyl)amine (imine₃tren) was prepared in order to stabilize high valent iron-oxido complexes. Iron complexes were synthesized in template reactions from iron(II) salts, tris(2-aminoethyl)amine (tren) and acetone. Due to the reversibility of the imine formation, complexes with different ligands were obtained depending on the reaction conditions. Three complexes, [Fe(imine₃tren)(OAc)₂] ( 1 ), [Fe(imine₃tren)(OAc)]OTf ( 2 ) and [(imine₃tren)₂Fe₂(F)₂](SbF₆)₂ ( 3 ), could be synthesized and structurally characterized. However, reactions with hydrogen peroxide, iodosobenzene or ozone did not lead to any kind of “oxygen adduct” complex that could be spectroscopically observed.     

Control of the J-Aggregation Phenomenon by variation of the N-alkyl-substituents

Cyanine dyes ( 1a–d ) with the 5,5′,6,6′-tetrachloro-1,1′-dialkyl-3,3′-di-(3-carboxypropyl)-benzimidocarbocyanine chromophore differing only in the chain length of their alkyl groups in 1,1′-position have been synthesized, spectroscopically characterized, and compared with 5,5′6,6′-tetrachloro-1,1′-diethyl-3,3′-di-(4-sulfobutyl)-benzimidocarbocyanine( TDBC ). In aqueous solution the dyes form J-aggregates which, depending on the alkyl group chain length, exhibit J-bands differing in spectral positions, bandwidth, and in the number of peaks.     

Heterogeneous distribution of chain mobility in nascent UHMWPE in the less entangled state

The structure of chain entanglements in the solid state is important for revealing the relationship of structure and properties of polyolefin. In this work, low-field solid-state ¹H NMR is used to study the chain dynamics of ultra-high molecular weight polyethylene (UHMWPE) in the solid state. It has been found that the relaxation distribution, analyzed by a multi-exponential inversion program, is an effective method to characterize the heterogeneous chain mobility. It is evidenced from the results that the UHMWPE in a less entangled state presents an obviously heterogeneous distribution of chain mobility in the non-crystalline phase, corresponding to its heterogeneous distribution of entangled points. In comparison, the commercial UHMWPE with a large number of entanglements shows a much more uniform mobility of the non-crystalline components. This heterogeneous distribution of chain mobility becomes even more critical after annealing the samples below the melting point, especially for the less entangled UHMWPE.     

Zur Radikalischen Copolymerisation ungesättigter Isocyanate mit Vinylchlorid

On the Free Radical Copolymerization of Unsaturated Isocyanates with Vinylchloride The free radical copolymerization of vinyl-, isopropenyl- and p-vinyl-phenylisocyanate with vinylchloride in mass and tetrahydrofurane solution at 50°C is investigated. The incorporation of the isocyanate monomers in the copolymers is favoured. These monomers effect a great decrease of the rate of copolymerization and a crosslinking of the formed homo- and copolymers, whose extent depends on the kind and the quantity of the incorporated monomers. The crosslinking is caused by the forming of isocyanurate units.     

Low-cost direct writing lithography system for the sub-micron range

Abstract

We have developed a fixed beam direct writing laser lithography system with a minimum feature size of 400nm at 457nm wavelength and a writing speed of 4·2mm/s with total system costs of less than 100 000 US$.     

Intrinsic isotopic C labelling of polyphenols

The intrinsic isotopic labelling of plants with ¹³CO₂ is an effective method to generate highly labelled compounds using photosynthesis and avoiding labour-intensive complex organic syntheses. In this study, the intrinsic isotopic labelling of polyphenols in parsley, spinach and peppermint is shown for the first time. The plants were grown in an atmosphere where ¹²CO₂ was replaced by ¹³CO₂, in order to generate highly labelled compounds. The total content of ¹³C as well as the individual polyphenols were analysed by Isotopic Ratio-MS and HPLC–Iontrap-MSⁿ.     

Influence of Zn2+ doping on the morphotropic phase boundary in lead-free piezoelectric (1 – x)Na1/2Bi1/2TiO3-xBaTiO3

A series of morphotropic phase boundary (MPB) compositions of (1–x)Na_1/2Bi_1/2TiO₃-xBaTiO₃ (x = 0.05, 0.055, 0.06, 0.065, 0.07), with and without 0.5 mol% Zn-doping was synthesized using the solid-state route. The samples were characterized using X-ray diffraction, dielectric analysis, and electromechanical measurements (piezoelectric d₃₃ coefficient, coupling factor k_p, mechanical quality factor Q_m, and internal bias field E_bias). The increase in the ferroelectric-relaxor transition temperature upon Zn-doping was accompanied by a shift of the MPB toward the Na_1/2Bi_1/2TiO₃-rich side of the phase diagram. Higher tetragonal phase fraction and increased tetragonal distortion were noted for Zn-doped (1 – x)Na_1/2Bi_1/2TiO₃-xBaTiO₃. In addition, ferroelectric hardening and the presence of an internal bias field (E_bias) were observed for all doped compositions. The piezoelectric constant d₃₃ and the coupling coefficient k_p decreased by up to ∼30%, while a 4- to 6-fold increase in Q_m was observed for the doped compositions. Apart from establishing a structure–property correlation, these results highlight the chemically induced shift of the phase diagram upon doping, which is a crucial factor in material selection for optimal performance and commercialization.