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.     

Wechselnde Bindungen in einem Zweikörpersystem mit trockener Reibung

Übersicht Betrachtet wird ein zwangserregtes Zweikörpersystem mit wechselnden Bindungen infolge trockener Reibung. Stationäre Bewegungen werden als Grenzfall instationärer Einschwingvorgänge berechnet. Abhängig von den Systemparametern ergeben sich drei typische Bewegungsformen. Ihnen entsprechen dauernde Haftzustände, wechselnde Haft-Gleitzustände oder dauernde Gleitzustände an der Berührfläche beider Körper.

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Intermittant constraints in a two-body-system with dry friction

Summary An externally excited two-body-system with intermittant constraints due to dry friction is considered. Stationary motions are calculated as limit cases of instationary transients. Depending on the parameters of the system, three typical modes are of interest. These correspond to permanent sticking, slipstick behaviour, or to permanent slipping in the contact surface of the bodies, respectively.

     

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.     

Palladium-catalyzed pseudo-domino cyclizations: An easy entry toward polycondensed pyrrolidone derivatives

A new type I palladium-catalyzed pseudo-domino process is developed, in which a single Pd-based catalytic system promotes two mechanistically unrelated, sequential catalytic cycles in chronologically distinct order. Suitable precursors undergo an allylic alkylation and a Heck coupling in sequence, affording polycondensed pyrrolidone derivatives. Depending on the starting precursors, intra/inter or doubly intramolecular processes can be obtained. The allylic alkylation process takes place always very smoothly. On the other hand, the Heck coupling turns out to be rather difficult either when the process is intermolecular, or when an intramolecular process generates polycondensed structures featuring three fused bonds connected to a common carbon atom. In such difficult cases, use of the Herrmann-Beller phosphapalladacycle allowed to catalyze the coupling. This study demonstrates also that allylic alkylations can be catalyzed by the Herrmann-Beller phosphapalladacycle.     

Mathematics achievement and interest in mathematics from a differential perspective

In this article, we present results of an empirical study with 500 German students of grades 7 and 8. The study focussed on students' mathematics achievement and their interest in mathematics as well as on the relation between these two constructs. In particular, the results show that the development of an individual student's achievement between grade 7 and grade 8 depends on the achievement level of the specific classroom and therefore on the specific mathematics instruction Interest in mathematics could be regarded a predictor for mathematics achievement Moreover, our findings suggest that the students show hardly any fear of mathematics independent of their achievement level.     

Analysis of concentration patterns in volcanic rocks: Insights into dynamics of highly explosive volcanic eruptions

In this contribution we present new data resulting from the analysis of concentration patterns of mixed juvenile fragments ejected by a highly explosive volcanic eruption that occurred on Salina Island (Aeolian Islands, Italy) and our aim is to identify the fluid-dynamic regime characterizing the magma mixing process. Concentration patterns are studied by calculating the power spectrum of concentration variability along transects crossing the magma mixing structures. Results indicate that the slope of power spectrum has an average value of about −5/3, according to Kolmogorov law of turbulence, and suggest that the magma mixing process, in the studied conditions, can be approximated by considering the passive scalar mixing hypothesis in homogeneous isotropic turbulent flow. These results represent a first step towards a better understanding of magma mixing processes associated to highly explosive volcanic eruptions and this first step is taken by studying concentration patterns in volcanic rocks by coupling petrological and non-linear dynamics methods.