Stepwise Adsorption of Alkoxy-Pyrene Derivatives onto a Lamellar,Non-Porous Naphthalenediimide-Template on HOPG

The development of new strategies for the preparation of multicomponent supramolecular assemblies is a major challenge on the road to complex functional molecular systems. Here we present the use of a non-porous self-assembled monolayer from uC₃₃-NDI-uC₃₃ , a naphthalenediimide symmetrically functionalized with unsaturated 33 carbon-atom-chains, to prepare bicomponent supramolecular surface systems with a series of alkoxy-pyrene ( PyrOR ) derivatives at the liquid/HOPG interface. While previous attempts at directly depositing many of these PyrOR units at the liquid/HOPG interface failed, the multicomponent approach through the uC₃₃-NDI-uC₃₃ template enabled control over molecular interactions and facilitated adsorption. The PyrOR deposition restructured the initial uC₃₃-NDI-uC₃₃ monolayer, causing an expansion in two dimensions to accommodate the guests. As far as we know, this represents the first example of a non-porous or non-metal complex-bearing monolayer that allows the stepwise formation of multicomponent supramolecular architectures on surfaces.     

Osmotic pressure of a nematic solution of polydisperse rod-like macromolecules

For a nematic solution of polydisperse rigid rods the osmotic pressure is proved to be independent of the length distribution and proportional simply to the total number density. This rule holds in the gaussian approximation to the Onsager theory. Its accuracy is demonstrated for bidisperse systems.     

Harmonisation of proficiency testing schemes

The harmonisation of proficiency testing (PT) schemes has been under debate for a long time. There are obvious reasons why harmonisation of the practices in PT would be beneficial. In many areas, there is still a belief that further harmonisation of practices in PT would improve the comparability of measurement data. In particular when two laboratories are to be compared that have not participated in a single PT, problems arise which allegedly can be overcome by further harmonisation of PT schemes. In practice, however, parties involved in PT are not always embracing the idea of harmonisation. With the results of two European projects in mind, a discussion is given on harmonisation aspects, and some considerations are given that may help to decide in practice whether harmonisation is likely to solve particular problems. The first project, the European Proficiency Testing Network (EPTN), is concerned with further harmonisation. The second European project (COEPT) aims at providing a basis to assess equivalence across proficiency tests, and explores the conditions under which such an assessment is feasible.

     

Die affinen Projektivitätengruppen der lokalkompakten zusammenhängenden Translationsebenen

Ohne ZusammenfassungHerrn Professor Hans Freudenthal zum 80. Geburtstag gewidmet     

Bounds for bounded motion around a perturbed fixed point

We consider a dissipative map of the plane with a bounded perturbation term. This perturbation represents e.g. an extra time dependent term, a coupling to another system or noise. The unperturbed map has a spiral attracting fixed point. We derive an analytical/numerical method to determine the effect of the additional term on the phase portrait of the original map, as a function of the bound on the perturbation. This method yields a value _c such that for< _c the orbits about the attractor are certainly bounded. In that case we obtain a largest region in which all orbits remain bounded and a smallest region in which these bounded orbits are captured after some time (the analogue of basin and attractor respectively).The analysis is based on the Lyapunov function which exists for the unperturbed map.     

Weighted Banzhaf values

The family of weighted Banzhaf values for cooperativen-person TU-games is studied. First we introduce the weighted Banzhaf value for an exogenously given vector of positive weights of the players. Then we give an axiomatic characterization of the class of all possible weighted Banzhaf values.     

Reduced and excited states of the intermediates (alpha-diimine)(C5R5)Rh in hydride transfer catalysis schemes: EPR and resonance Raman spectroscopy, and comparative DFT calculations of Co, Rh and Ir analogues

The electronic structures of the highly air-sensitive intermediates (N[caret]N) (C(5)Me(5))Rh, (N[caret]N = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym), 2,2'-bipyrazine (bpz) and 3,3'-bipyridazine (bpdz)) of hydride transfer catalysis schemes were studied through resonance Raman (rR) spectroscopy and through EPR of the reduced forms [(N[caret]N) (C(5)Me(5))Rh](.-). The rR results are compatible with a predominant MLCT character of the lowest excited states [ (N[caret]N) (C(5)Me(5))Rh]*, and the EPR spectra of the reduced states reveal the presence of anion radical ligands, (N[caret]N) (.-), coordinated by unusually electron rich rhodium(i) centres. The experimental results, including the assignments of electronic transitions, are supported by DFT calculations for the model compounds [(N[caret]N)(C(5)H(5))Rh](o)/(.-), (N[caret]N) = bpy or bpym. The calculations confirm a significant but not complete mixing of metal and ligand orbitals in the lowest unoccupied MO which still retains about 3/4 pi* (N[caret]N) character. DFT calculations on (bpy)(C(5)H(5))M and [(bpy)(C(5)H(5))ClM](+), M = Co, Rh, Ir, agree with the experimental results such as the differences between the homologues, especially the different LUMO characters of the precursor cations in the case of Co-->d(M)) and Rh or Ir (-->pi*(bpy)).     

Thermal decomposition of hydrotalcitewith hexacyanoferrate(II) and hexacyanoferrate(III) anions in the interlayer

The thermal decompositions of hydrotalcites with hexacyanoferrate(II) and hexacyanoferrate(III) in the interlayer have been studied using thermogravimetry combined with mass spectrometry. X-ray diffraction shows the hydrotalcites have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. XRD was also used to determine the products of the thermal decomposition. For the hydrotalcite decomposition the products were MgO, Fe₂O₃ and a spinel MgAl₂O₄. Dehydration and dehydroxylation take place in three steps each and the loss of cyanide ions in two steps.