This habilitation thesis describes the syntheses and characterizations of mostly new metal-rich cluster compounds of early transition elements. It is devided into 4 parts. The first part describes the syntheses and solid-state X-ray structures of a total of 14 mixed-halide (iodide-chloride) zirconium cluster phases, which crystallize in 9 different (some novel) structure types. All these cluster phases contain octahedral Zr6Z-units that are centered by an interstitial atom Z. Phase widths and relations between the differend structure types are discussed. The second part deals with molecular (soluble) zirconium cluster phases which are excised from solid-state precursors. It is shown that liquid mixtures of 1,3-dialkylimidazolium bromide and AlBr3 as well as molten 18-crown-6 are useful solvents for molecular zirconium cluster compounds. The syntheses and single crystal X-ray structures of 3 new materials are detailed. Furthermore, from the reaction of an iron containing Zr-cluster phase with KSCN crystals have been obtained from which a single crystal X-ray structure analysis shows that they contain a high symmetry Fe-cubane cluster. The third part of this thesis is concerned with theoretical investigations (Extended-Hckel band structure calculations) of a series of monoclinic phases which contain double-octahedral chains of rare earth metal clusters of the general formula RE3I3Z (RE = rare-earth metal atoms). The results of the electronic band structure calculations show that the observed structural variations within this series depend largely on the difference of the orbital energies of the rare earth metals and the interstitials. In the last part the phase pure synthesis of Nb21S8 and measurements of physical properties (electrical conductivity and magnetical susceptibility) as well as results from electronic band structure calculations (LMTO) are described. The property measurements show that this metal rich sulfide becomes superconducting below 3.7(2) K. The results from the electronic band structure calculations indicate the existence of an arrangement of electronic levels ("fingerprint") which favors the formation of superconducting Cooper pairs.

The swelling behaviour of water sensible, chemically crosslinked polyurethanes has been examined in water and mesogenic solvents. The experimental swelling curves have been described with generally known network theories . The swelling curve in a polymer solution has been determined for the first time dependent on temperature. Additionally temperature dependent membrane-osmosis experiments on the system polyethyleneoxide/water have been performed.

This work is subdivided in three chapters. In the first chapter the synthesis of a 7,7'-bridged 1,1'-Biisoquinoline by a Pomeranz-Fritsch-Reaction is described. This molecule was seperated in its atropisomers which racemice in solution. The influence of the solvent character to the rate of racemization was investigated. It has been shown that the more polar and the more protic the solvent is the higher is the rate of racemization. The second chapter introduces an easy synthetic route to 6-substituted Benzimidazo[2,1-a]isoquinolines and in the single case of a Furyl-substituent to Isoindolo[2,1-a]quinoxalins. The starting materials, ortho-Alkynyl-substituted Benzaldehydes, are prepared by Sonogashira-Coupling of the Bromobenzaldehydes with different substituted terminal Alkynes. The reaction of o,o'- Bis(phenylethinyl)-substituted Benzil with Hydroxylamine Hydrochloride leads to a rearranged Benzofluorenon. The formation is explained by a domino process including a cyclization-step, a Hetero-Diels-Alder reaction and the final rearrangement. In the third chapter the stereochemical outcome of the McMurry reaction is investigated depending on the length of a tether between the meta and meta'-position of an Bisbenzaldehyde. Only the short dioxapentandiyl tethered Bisbenzaldehyde forms streoselectiv the cis-product. Starting with the dioxaoctandiyl- or dioxatetradecandiyl-tethered Bisbenzaldehydes the thermodynamical more stable trans products are obtained. In a second part the regioselectivity of the oxidative photocyclization of these McMurry-products, leading to tethered Phenathrenes, has been investigated. The dioxapentandiyl- and the dioxaoctandiyl-substituted Stilbenes leads regioselectiv to the 4,5-disubstituted Phenathrenes. Whereas the longer dioxatetradecandiyl-tether allows a change in the product ratio and the 2,5-disubstituted Phenanthrene is obtained as the major product. In all cases no 2,7-Phenanthrene could be detected.

In the theoretical part of this dissertation theintroduction of the thermodynamics of mixtures is followed by the basicknowledge of lightscattering. The correlation between thermodynamics atthe one hand and lightscattering at the other is demonstrated. In the apparativeand practicel part the development, build and handeling of the high pressurecell and the carrying out of the light scattering experiments are shown.In the part "results and discussion" the interesting and partly surprisingresults are presentet and discussed.

Ni/Mg/Al containing anionic clays of hydrotalcite-type structure with varying Ni/Mg ratio and constant Al content were synthesised by coprecipitation. Their composition and structure was determined by elemental analysis, XRD, TG-MS and DSC. Their calcination at 700-1000°C resulted in the transformation into the corresponding mixed metal oxides, with their structure depending on the calcination temperature. Temperature programmed reduction/oxidation and high temperature XRD studies were applied to study their reducibility, Ni dispersion and the oxidation of the formed metallic nickel particles. The partial oxidation of propane to syngas could be successfully performed at temperatures between 600 and 900°C over reduced Ni containing catalysts. The conversion of propane and the yield of syngas increased with increasing reaction temperature. The catalysts with a low to medium Ni content exhibited better catalytic performance than those with a higher Ni content or a conventional steam reforming catalyst used as reference. Coking was found to decrease with increasing reaction temperature and to increase with increasing Ni content. Since several factors characterising the catalysts (BET surface area, Mg content and available Ni surface) follow the same or the opposite trend with the Ni content, it was impossible to differentiate between these properties and their effect on the catalyst performance or coking. By the use of the best catalyst an at least two-fold increase in the yield of carbon monoxide and eight-fold increase in the yield of hydrogen was observed compared with the non-catalytic reaction. Further investigations were performed to study the influence of the feed ratio and the space velocity.

Due to legal requests in future the identity control of products will not only be required in pharmaceutical industry but also in chemical industry. Therefore the demands on the analytical methods are very high. The company Merck realized an identity control tool by combining NIR and Raman spectroscopy. This Tool is suited for identification of a broad range of organic and inorganic substances. In this work different chemometric methods and data pretreatments were tested. The NIR and the Raman library have been optimized and the validation results visualized. Alternatives as binary coding and wavelet transformation, which lead to data compression at the same time, were tested

The possibility of synthesis of (poly-)chalcogenide and chalcogenolate ions to manganese, iron and cobalt was expanded with the introduction of the donor ligand carbon monoxide. The metal atoms get than greater coordination numbers. So it was possible to synthesise new metal frameworks, p. e. Co11E7 in the complexes [Ph4P]2[Co11Se7(CO)10] and [Ph4P]2[Co11Te7(CO)10], in which the cobalt atoms built a inner centred pentagonal prism. In the examined reaction systems Mn2(CO)10/Na2Sex/Kat, Fe(CO)5/Na2Ex/Kat and Co2(CO)8/Na2Ex/Kat (E = Se or Te; x = 1 or 2; Kat = Ph4PCl or PPNCl) succeeded the synthesis of [Co6Se8(CO)6]-/2-anions as first anionic clusters of the M6E8L6 class. The difference between the new [Co6Se8(CO)4]- anion and the M6E8L6-complex class is the extraordinary compressed Co6-oktaeder and considerable shorter Co-Co-distances. In addition to the higher mentioned compounds it was possible to synthesise and characterize unambiguous with the aid of single crystal x-ray crystallography the following complexes: [Ph4P]2[Fe3Te(CO)9]; [Ph4P][Fe3EH(CO)9] für E=Se,Te; [Ph4P]2 [Fe4Te2(CO)14]; [Ph4P]2 [Fe6Se6(CO)12]; [Ph4P]2 [Mn3Se2(CO)9]. Worth mentioning is also the unusual square pyramidal coordination of the manganese atom in the [Ph4P][Mn(CO)5] crystal. Until now were only penta carbonyl complexes known with a trigonal bipyramidal coordination.

In the following thesis the thermotropic phase transition behaviour and structure-property-relations of semiflexible polyesters were investigated. These materials can be used in fibre optical blood-pressure sensors as resonator materials in a Fabry-Perot-Interferometer. PVT-measurements were carried out to determine the thermodynamic parameters alphaV(T) and kappa(P), and the validity of the Ehrenfest equations at glass transition temperatures was verified. These latter investigations showed no thermodynamic second order transition. By using alphaV(T) and kappa(P) for the calculation of the resonator-length-difference, the temperature- and pressure behaviour of the investigated polyesters was simulated. This simulation showed that small variations in the resonator length from increasing pressure agrees with the empirically determined values. An increasing number of methylene groups in the sidechain of the spacer molecule resulted in decreased melting- and glass transition temperature, which revealed the possibility to prepare thin polymer-films with 5-10 micrometer in diameter at low temperatures.

The present work describes the use of Ion Mobility Spectrometry (IMS) as a detection method for specific thermolysis products with respect to the early recognition of fires. By using additional analytic methods such as simultaneous differential thermal analysis/thermogravimetry (DTA/TG), gas chromatography/mass spectrometry (GC/MS) and Infrared spectrometry (IR) the specific thermolysis products depent on the temperature of the fire load were characterized and identified. While considering possible interference like e.g. varying atmospheric humidity the limits of detection and determination of the detectable gasses by IMS were determined.

In the context of this work, a computer program is developed for the simulation of the interference fringe patterns of laboratory-scale pool-fires of organic fuels. With the help of this simulation tool, the formation as well as the dynamics of typical structural components in the interference fringe patterns in the flame neck and the flame plume are modelled. A model conception for the formation of the interference fringe patterns in the flame plume is developed. The temperature field is modelled as a relatively cold convection column, into which a large amount of statistically distributed hot volume elements with gaussian temperature distribution is inserted. The simulation with this model conception shows the typical structure of the measured interference fringe patterns in the flame plume with good congruence. The physical meaning of the velocity of the interference fringe pattern shift within the areas of the flame neck and the flame plume is examined. It is shown in particular that the temporally averaged shifting velocity in vertical direction in the flame neck can be identified as a temporally averaged ascent rate of the flame gases within the region of the thermal boundary layer. For the flame plume, the shifting velocity can be interpreted as a flow velocity averaged over time and the line of sight.