The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Notiz über Parachloraldehyd

Ohne Zusammenfassung     

Restorations of punctured languages and similarity of languages

Punctured languages are languages whose words are partial words in the sense that the letters at some positions are unknown. We investigate to which extent restoration of punctured languages is possible if the number of unknown positions or the proportion of unknown positions per word, respectively, is bounded, and we study their relationships for different boundings. The considered restoration classes coincide with similarity classes according to some kind of similarity for languages. Thus all results we can also formulate in the language of similarity. We show some hierarchies of similarity classes for each class from the Chomsky hierarchy and prove the existence of linear languages which are not δ ‐similar to any regular language for any δ < ½. For δ ≥ ½ this is unknown but it could only be possible in the case of non‐slender linear languages. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Untersuchungen über Papaverin

Ohne Zusammenfassung     

4-Amino-imidazole durchThorpe-Cyclisierung

The alkylation of arylaminomethylenecyanamides1 or cyano-imidothiocarbamates2 with -halogen carbonyl compounds followed by base catalysed cyclization yields substituted 4-amino-imidazoles4. Imidazo[4,5-d]pyrimidones5, 6 and imidazo[4,5-b]pyridines7 can be obtained from4.     

The electrocapillarity of polyacrylates

Summary The electrocapillary properties of polyacrylic acid have been studied by two methods. Exploratory measurements have been made of the effect of the polymer on the differential capacity of a mercury drop in 0.1 m sodium perchlorate. They showed that the polymer was strongly adsorbed over a wide range of potentials but that it did not appear to form a monolayer. The surface excess of polymer obtained from drop weight data showed a maximum at very low concentrations and then a decline at higher concentrations. The bulk of the work was carried out by making surface tension measurements, using a sessile mercury drop, in solutions of a fraction of polyacrylic acid (mol. wt. 7.02×10⁴) in potassium chloride at 0.01, 0.1, 0.2, and 0.5 m at 25°C.The data have been used to evaluate the surface excesses of the polymer and of the inorganic ions. The distribution of K⁺ and Cl^– in the electrical double layer and the contact adsorption of Cl^– on the mercury were very little affected by the presence of the polymer. The surface excess of polymer was always found to be greatest at low concentrations, to decrease steeply at first as the concentration was increased and then to decrease more slowly at higher concentrations.Possible explanations of this behaviour are discussed and it is concluded that the rapid decrease is a consequence of molecular weight dispersion and the stronger adsorption of high molecular weight polymer. The slow decrease in surface excess at higher concentrations may be a result of configurational changes of the polymer molecules.Surface pressure data show that, despite this decrease in the surface excess, the surface coverage reaches a high level at very low polymer concentrations and then continues to increase slowly as the concentration of polymer is increased. This apparent contradiction is due to changes in configuration of the adsorbed polymer molecules. At higher bulk concentrations the chain configurations are more compact and each adsorbed molecule makes more contacts with and so occupies a greater area of the mercury surface than at low concentrations.The conclusion is reached that the surface excess of polymer is mostly contained in a layer probably more than 1000 Å thick. It consists of a concentrated and entangled mass of polymer chains. Relatively few of these chains are in contact with the mercury at any istant. The concentration in this surface layer decreases steadily with increasing distance from the mercury surface and it merges without discontinuity into the bulk solution.With 10 figures in 22 details     

Nachweise verwandter Elemente nebeneinander in einem Tropfen. II. Mitteilung: Der mikrochemische Nachweis von Aluminium und Beryllium mittels Ammoniummolybdats

Zusammenfassung Entgegen den Auffassungen von van Zijp über den von ihm veröffentlichten Nachweis des Aluminiums mit Ammoniummolybdat wurde gezeigt, daß ein derartiger Nachweis Empfindlichkeit und Störungsfreiheit in hohem Grade vereint.Der Nachweis durch Ammoniummolybdat konnte auf Beryllium ausgedehnt werden. Eine Reihe von Versuchen zeigte, daß Aluminium- und Berylliummolybdat in zwei verschiedenen Krystallformen ohne gegenseitige Beeinträchtigung selbst nebeneinander auszukrystallisieren vermögen.Es ist mir eine angenehme Pflicht, Herrn Prof. Dr. Wilhelm Böttger für sein stets färderndes Interesse und für die mikrochemische Arbeitsmäglichkeit überhaupt zu danken. Zu Dank verpflichtet bin ich auch der Fa. Otto Perutz, München für die freundliche überlassung von Pervola-Platten zu den Mikrophotographien.     

Untersuchungen an reagenzien zur photometrischen zinnbestimmung

The formation of complexes between tin(IV) and o-diphenols, and o-hydroxyquinones, has been studied spectrophotometrically. Simple o-hydroxyquinones do not react with tin(IV), chloranilic acid gives an SnR₂ complex, and o-diphenols give SnR₃ complexes. The reactions of tin(IV) with hydroxyxanthene dyes to give coloured products were considered for their possible analytical utility: the pH range, absorption spectrum, solubility and composition of the complexes were investigated, and the stability constants determined. Analytical procedures have been developed for tin and checked for precision and sensitivity: gallein and hydroxyhydroquinonephthalein (dihydroxyfluorescein) are to be recommended.