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     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Synthesis and Characterization of Silica@Copper Core–Shell Nanoparticles: Application for Conjugate Addition Reactions

Silica@copper (SiO₂@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO₂@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity.     

Particle Characterization by Projected Area Determination

The projected areas of non-spherical particles do not represent an unambiguous particle characteristic. Depending on the orientation towards a constant observational direction, different projected areas result. The spectrum of all projected area values of a particle, if determined representatively, gives the probability with which a certain value is obtained by a single measurement. In this work, the frequency distributions of different examples of test objects were both calculated and measured. The objects were a cube, a rectangular parallelepiped and also three model agglomerates consisting of spheres of the same size. Instead of just one projected area, during each measuring procedure three projected areas from three orthogonal directions can be obtained. A mean value is then calculated to reduce the ambiguity of the particle characteristic and enhance the resolution. A suitable measurement set-up is introduced. The results of calculation and measurement are compared for observation from just one direction and also simultaneous observation from three directions. The frequency distributions of the equivalent diameters of the particle projected areas show a characteristic trend of the total curve with remarkable properties. The simultaneous measurement of three values from mutually orthogonal directions and their mean value calculation result in a much narrower distribution. In this case, a non-sphericity factor can additionally be calculated, whose frequency distribution contains information in a characteristic manner about the degree to which the particle shape differs from a sphere.     

Minimum boundary touching tilings of polyominoes

We study the problem of tiling a polyomino P with as few squares as possible such that every square in the tiling has a non‐empty intersection with the boundary of P . Our main result is an algorithm which given a simply connected polyomino P computes such a tiling of P . We indicate how one can improve the running time of this algorithm for the more restricted row‐column‐convex polyominoes. Finally we show that a related decision problem is in NP for rectangular polyominoes. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of poly(vinyl alcohol)‐graft‐[poly(D,L‐lactide)/poly(D,L‐lactide‐co‐glycolide)] hydrogels

Poly(D ,L ‐lactide) and poly(D ,L ‐lactide‐co‐glycolide) with various composition and with one methacrylate and one carboxylate end group were synthesized and grafted onto poly(vinyl alcohol) (PVA) via the carboxylate group. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator. The polymer networks were characterized by means of NMR and studied qualitatively by means of IR spectroscopy. The influence of the glycolide content in the polyester grafts and of the number of ester units in the grafts on thermal properties and swellability were studied as well. The high swellability in water is characteristic of all hydrogels. Differential scanning calorimetry (DSC) showed a single glass transition temperature that occurs in the range between 51 and 69 °C. Thermogravimetric analysis (TGA) of the networks showed the main loss in weight in the temperature range between 290 and 370 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4536–4544, 2007