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.     

An eulerian trail traversing specified edges in given order

The following results are proved in this paper. Let G be a 2k-edge-connected eulerian graph. (i) For every set {e₁, e₂, ?, e_2k+1} ? E(G) there is an eulerian trail T of the form e₁, e₂, ?, e_2k+1, ?. (ii) For every set E* = {e₁, e₂, ?, e_k} ? E(G) there is an eulerian trail T = e₁, ?, e₂, ?, e_k, ? in which the elements of E* are traversed in accordance with a prescribed orientation. © 1995 John Wiley & Sons, Inc.     

Methodology for the preparation of C1-monoalkylated 1,2-dihydro[C70)] derivatives: formation of the "other" regioisomer

Deprotonation of 1,2-C(70)H(2) with TBAOH, followed by alkylation with methyl bromoacetate, results in formation of a C1-monoalkylated 1,2-dihydro-C(70) derivative. The position of the alkyl group (C1) was established by NMR spectroscopy and comparison with literature spectra of C2-monoalkylated analogs. Presumably, C1-alkylation is the major process due to selective deprotonation of 1,2-C(70)H(2) at C1. Substitution of benzyl bromide for methyl bromoacetate results in rapid dialkylation, unless the amount of base is carefully controlled, in which case C1-monobenzylation is the major process. This methodology for alkylation at C1 is complimentary to methods for the C2-monoalkylation of C(70) with Zn and methyl bromoacetate.     

Stereochemie von Metallocenen, 40. Mitt.

Starting from optically active methylferrocene-- and--carboxylic acids (1 a and1 b) of known absolute configuration and enantiomeric purity about 15 chiral ferrocenes (of each isomeric series— and ) were obtained by suitable ligand transformations. Thereby (almost) all possible chiral combinations of the ligands CH₃, COOH (COO^–), COOCH₃, CN and NH₂ (NH₃ ⁺) were accessible which are necessary for a potential test of approximations of chirality functions for compounds with basic symmetry C_5v. The chiroptical properties of these disubstituted ferrocenes are recorded.Preliminary tests using a shortened Ansatz revealed large discrepancies between calculated () and found [M]_D-values. Possible reasons for this failure are discussed.

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61. Mitt. über Ferrocenderivate

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39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).

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60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975).     

Wirkungsgrade in der Welt des Lebens und der Technik

Zusammenfassung Um der oft gehörten Meinung entgegenzutreten, die energetischen Wirkungsgrade lebender Organismen seien wesentlich höher als die technischer Verfahren, werden entsprechende Werte miteinander verglichen. Der sehr niedrige Wirkungsgrad der Photosynthese zusammen mit der kleinen Energiedichte der Sonnenstrahlung erzwang ab einer kritischen Größe die Aufspaltung in Energiesammler, die Pflanzen, und Verbraucher chemischer Energie, den Tieren. Dank den 10 mal höheren Wirkungsgraden in der Technik, lassen sich Solarmobile bauen, die von der auf sie fallenden Sonnenstrahlung angetrieben werden. Wegen des Multiplikationsgesetzes der Teilwirkungsgrade ergeben sich sowohl für die Speicherung der Sonnenenergie in den fossilen Brennstoffen wie in der Nahrungskette extrem niedrige Wirkungsgrade.

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Efficiencies in the world of life and in engineering

One often hears the opinion, that the efficiencies in the world of life are higher than in engineering. To disprove this, many values of efficiency of corresponding processes are compared. The very low efficiency of photosynthesis in living plants together with the low density of solar radiation has led the world of life to split into collectors of energy, the plants, and consumers of chemical energy, the animals. Thanks to the ten times higher efficiencies of solar cells, it is possible, to produce solar mobiles, vehicles that move driven by solar radiation.

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Herrn Prof. Dr.-Ing. U. Grigull zum 75. Geburtstag gewidmet     

Umsetzung von hydrobromiertem 1,4-Polybutadien mit lithiumorganischen Verbindungen

Ohne ZusammenfassungMit 1 Abbildung und 1 Tabelle     

Die Schmelzdiagramme der Systeme CsN3/Zn(N3)2 und KN3/Zn(N3)2

The phase diagrams of the systems CsN₃/Zn(N₃)₂ and KN₃/Zn(N₃)₂ have been obtained employing the microscopic technique ofL. Kofler andA. Kofler. Within the system CsN₃/Zn(N₃)₂ three eutectics at 148°C, 142°C, and 210°C were found. Besides Cs₂Zn(N₃)₄, melting incongruently in the interval 153°C to 170°C, there exist two further compounds of the most probable composition Cs₃Zn₂(N₃)₇ and CsZn₂(N₃)₅, melting congruently at 170°C and 210°C, resp. In the system KN₃/Zn(N₃)₂ there exist two eutectics at 203°C and 172°C and two compounds, one of them, i.e. K₂Zn(N₃)₄, melting congruently at 206°C, the other one, with composition KZn₃(N₃)₇ or KZn₄(N₃)₉, melting incongruently at 210°C.

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Mit 8 Abbildungen

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Herrn Professor Dr.Heribert Grubitsch zum 70. Geburtstag gewidmet.     

13C-NMR-spektren stereoisomerer 1,4-dialkylspiro[4.5]decan-derivate

The ¹³C NMR spectra of a series of 7-substituted 1,4-dialkylspiro[4.5]decanes and of suitable reference compounds are assigned and the derived substituent effects upon the chemical shifts are discussed. In particular, consideration of γ and δ-effects allows the differentiation between 1,4-cis- and 1,4-trans-compounds. Furthermore, the (relative) configuration of the chiral spiroatom C-5 is determined.