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  • Articles: DFG German National Licenses  (5)
  • Solid-state reactions  (3)
  • Fullerides  (2)
  • 1
    Electronic Resource
    Electronic Resource
    On the Geometry of the Fulleride Dianion C602- in Crystalline Fullerides - Syntheses and Crystal Structures of [M(NH3)6]C60 · 6 NH3 (M = Mn2+, Cd2+) (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1183-1186 
    Details
    ISSN: 1434-1948
    Keywords: Fullerides ; Crystal structure analysis ; Jahn-Teller effect ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fullerides [M(NH3)6]C60 (M = Mn2+, Cd2+) have been synthesized by ion exchange in liquid ammonia and analyzed by X-ray single-crystal diffraction. With both complex cations the C602- units are in fixed orientations, and their geometries have been determined with good accuracy. An inspection of the fulleride dianions with respect to geometric deformations in the title compounds and three further independent determinations has led to the conclusion that no significant static Jahn-Teller distortion is present.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 2
    Electronic Resource
    Electronic Resource
    Über die Elektrokristallisation von Fulleriden (1995)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 982-986 
    Details
    ISSN: 0044-2313
    Keywords: Fullerides ; crystal structure ; C60- anion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrocrystallization of FulleridesThe fullerides P(C6H5)4C60 · P(C6H5)4Cl, P(C6H5)4C60 · P(C6H5)4Br und As(C6H5)4C60 · As(C6H5)4Cl have been prepared by electrocrystallization. Single crystal structure determinations have shown them to be isostructural in space group I4/m with lattice constants a = 12.5731(9), c = 20.142(3) Å; a = 12.5378(10), c = 20.606(5) Å; a = 12.6003(11), c = 20.377(4) Å, respectively. Spectroscopic and magnetic investigations prove the existence of a C60- anion, showing orientational disorder in all three fullerides.
    Notes: Die Fulleride P(C6H5)4C60 · P(C6H5)4Cl, P(C6H5)4C60 · P(C6H5)4Br und As(C6H5)4C60 · As(C6H5)4Cl wurden durch Elektrokristallisation erhalten. Die Strukturbestimmung an Einkristallen ergab, daß alle drei Verbindungen isotyp in der Raumgruppe I4/m mit den folgenden Gitterkonstanten kristallisieren: a = 12,5731(9), c = 20,142(3) Å; a = 12,5378(10), c = 20,606(5) Å; a = 12,6003(11), c = 20,377(4) Å (Die Zahlen beziehen sich auf die Fulleride in der oben angegebenen Reihenfolge). Spektroskopische und magnetische Untersuchungen belegen die Existenz eines C60--Anions, das im Kristall orientierungsfehlgeordnet vorliegt.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19956210615
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Homoatomic d10-d10 Interactions: Their Effects on Structure and Chemical and Physical PropertiesDedicated to Professor Rudolf Hoppe on the occasion of his 65th birthday (1987)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 26 (1987), S. 1098-1110 
    Details
    ISSN: 0570-0833
    Keywords: Bond theory ; Solid-state reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distinction between valence electrons and essentially inactive core electrons is the basis of many classifying concepts in chemistry. However, it has recently been recognized that this is an oversimplification and should, at least in some areas of chemistry, be modified. Many cases are known where cations with closed d10 configurations are subject to homoatomic interactions that influence structure and properties. A characteristic and surprisingly uniform structural feature (e.g., of a number of compounds containing monovalent coinage metals) is a clusterlike assembly of d10 cations that corresponds in geometry and bond lengths to fragments of the metal structures themselves. Further evidence for a special type of bonding in such compounds is provided by their physical properties; for example, the absorption in the UV/VIS region shows a drastic redshift and the compounds are often conductors or semiconductors. The d electrons in such cases have obviously lost their pure “core” nature. All bonding models so far proposed for such systems involve mixing of higher orbitals.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.198710981
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    Paper (German National Licenses)
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  • 4
    Electronic Resource
    Electronic Resource
    Volume Effect or Paddle-Wheel Mechanism - Fast Alkali-Metal Ionic Conduction in Solids with Rotationally Disordered Complex AnionsDedicated to Professor Karl Heinz Büchel on the occasion of his 60th birthday (1991)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 30 (1991), S. 1547-1558 
    Details
    ISSN: 0570-0833
    Keywords: Alkali metals ; Solid-state reactions ; Ion conductors ; Conducting materials ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transport phenomena in the solid state are of equal importance in basic research and practice. In the past two decades particular interest has been directed towards so-called “fast” or “super” ionic conductors because of their attractive potential applications. We have synthesized highly conductive alkali-metal ionic conductors based on ionic crystals in which, on the one hand, high concentrations of the charge carriers can be realized by doping (point defects in the cation substructure) and, on the other, the activation energy of the interchange of sites is decreased by translationally fixed but rotationally mobile complex anions. Mixed crystals with Na3PO4 or Na3AlF6 structures have proven especially suitable in this connection. With the object of establishing a broader experimental foundation for clarifying the controversially discussed question of whether the higher free transport volume or the rotational motion of the anions is responsible for the high cation mobility in these rotary phases we have systematically varied the type of anions and concentration of defects and monitored the resulting changes in conductivity. Although the macroscopical characteristics investigated are not suitable for explaining mechanisms in detail at the atomic level, the results afford clear support for the assumption of a “paddle wheel mechanism”; but also effects of the enlarged transport volume are not to be disputed. Both these effects enhancing the cationic conductivity are concomitantly operative in amounts varying from system to system; they cannot be totally separated from each other. Seen in this light, the alternative, “volume effect” or “paddle wheel mechanism,” is not as sharply defined as was previously discussed.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.199115471
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    Paper (German National Licenses)
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  • 5
    Electronic Resource
    Electronic Resource
    First Step Towards Planning of Syntheses in Solid-State Chemistry: Determination of Promising Structure Candidates by Global Optimization (1996)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 1286-1304 
    Details
    ISSN: 0570-0833
    Keywords: computer chemistry ; solid-state structures ; structure prediction ; synthesis planning ; Computer chemistry ; Solid-state reactions ; Solid-state structures ; Solid-phase synthesis ; Structure prediction ; Synthesis design ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented here that allows, in principle, the prediction of the existence and structure of (meta)stable solid compounds. It is based on a set of adjustable modules that are applied to the study of the energy function of the chemical system of interest. The main elements are a set of routines for global optimization and local minimization, as well as algorithms for the investigation of the phase space structure near local minima of the potential energy, and the analysis and characterization of the structure candidates. The current implementation focuses on ionic compounds, for which empirical potentials are used for the evaluation of the energy function in the first stage, and a Hartree-Fock algorithm for refinements. The global optimization is performed with a stochastic simulated annealing algorithm, and the local minimization employs stochastic quenches and gradient methods. The neighborhoods of the local minima are studied with the threshold algorithm. The results of this approach are illustrated with a number of examples: compounds of binary noble gases, and binary and ternary ionic compounds. These include several substances that have not been synthesized yet, but should stand a fair chance of being kinetically stable, for example further alkali metal nitrides besides Li3N, as well as Ca3SiBr2 or SrTi2O5.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.199612861
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    Paper (German National Licenses)
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