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  • General Chemistry  (5)
  • Organic Chemistry  (4)
  • Self-assembly  (1)
  • 1990-1994  (9)
  • 1994  (4)
  • 1990  (5)
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  • 1990-1994  (9)
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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reductive electrocrystallization at a constant current density (11.0-11.5 μA/cm2) of millimolar solutions of [M(bpy)3](PF6)2, where M = Fe, Ru, or Os, and bpy = 2,2′-bipyridine in acetonitrile containing 0.1M Bu4NPF6 results in the formation of dark crystals on the Pt cathode. The crystals grow as long, thin, and shiny needles having a hexagonal cross section of 0.1-0.5 mm in diameter. Combustion microanalyses results are consistent with the composition for [Fe(bpy)3], [Ru(bpy)3], and [Os(bpy)3]. In addition, the chromophores are conserved, as confirmed by recording both the electronic and the 1H-NMR spectra after reoxidation of the electrocrystals in humid air. The spectra are identical to those for authentic samples of [Fe(bpy)3]2+, [Ru(bpy)3]2+, and [Os(bpy)3]2+. A ratio of 2.0 ± 0.1 e-/molecule is observed upon completion of the controlled potential electrolysis of a solution of [M(bpy)3]2+, which results in the precipitation of a dark solid and the almost complete fading of the color of the original solution. Unexpectedly, the crystals do not exhibit an ESR signal. These data indicate the formation of novel materials, crystalline [Fe(bpy)3], [Ru(bpy)3], and [Os(bpy)3].
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 73 (1990), S. 1149-1162 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthetic procedures have been developed for the preparation of ligands bearing two to six pendent, unsubstituted or substituted 2, 2′-bipyridine groups attached to acyclic (tripode, tetrapode) and macrocyclic (triazanonade-cane, cyclam, hexacyclen, bis(bipyrido)hexaazamacrocycle) polyamines. Ligands 1-5 have been obtained in high yield by condensation of 6-(bromomethyl)-2, 2′-bipyridine (9b) with the corresponding amines in the presence of NaOH, H2O, and MeOH. Ligands 6-8 have been prepared in good yield by condensation of 9b or the di- or tetrasubstituted mono (bromomethyl) bipyridine 10b or 11b, respectively, with the corresponding amines in the presence of Na2CO3 and MeCN. Ligand 1 forms hemi-cage complexes with RuII, FeI, CrII, and CrIII cations and trinuclear complexes with [RuCl2(bpy)2] and [ReCl(CO)5]. Tetrapode 2 and hexapode 4 gave tetranuclear and dinuclear complexes, respectively, by reaction with Fe11 salts. These complexes possess a variety of interesting physical and chemical properties.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Eu3+ complexes of the tripode and tetrapode ligands 1 and 2, respectively, containing 2,2′-bipyridine coordinating units have been prepared. The UV absorption and luminescence spectra, lifetimes, and quantum yields have been measured under a variety of experimental conditions. The contributions of different paths to the decay of the luminescent excited state are evaluated, and the structures of the complexes are discussed on the basis of spectroscopic and photophysical data.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The lithium and europium(III) cryptates of a macrobicyclic ligand 1 incorporating the 3,3′-biisoquinoline 2,2′-dioxide 2 have been prepared. The Eu(III) complex [Eu(2)2]Cl3 has also been obtained. These Eu(III) complexes present characteristic 1H-NMR spectra containing markedly shifted resonances. They are strongly luminescent; the emission spectra, quantum yields, and lifetimes have been determined.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 102 (1990), S. 1347-1362 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Der erste Schritt der selektiven Bindung eines Substrats an einen Rezeptor unter Bildung eines supramolekularen Verbandes (eines „Übermoleküls“ oder „Überkomplexes“) ist die molekulare Erkennung, die durch die in den beteiligten Molekülen gespeicherte Information ermöglicht wird. Die Funktionen von supramolekularen Einheiten umfassen sowohl Erkennung als auch Katalyse und Transport. In Verbindung mit der Organisation von molekularen Einheiten zu geordneten Systemen eröffnen sich so Wege zu molekularen und supramolekularen Funktionseinheiten für die Informationsverarbeitung und Signalerzeugung. Die Entwicklung solcher Funktionseinheiten erfordert die Herstellung von Molekülen, die bestimmte Funktionen (z. B. Photoaktivität, Elektroaktivität, Ionenaktivität, Thermoaktivität oder Chemoaktivität) erfüllen können und die außerdem für den Einbau in geordnete Systeme geeignet sein müssen. Molekulare Funktionseinheiten zur Lichtumwandlung und zur Ladungstrennung konnten mit photoaktiven Cryptaten verwirklicht werden, die aus Rezeptoren mit lichtempfindlichen Gruppen wie Bipyridinen und Porphyrinen bestehen. Zum Transport elektronischer und ionischer Signale sind elektroaktive und ionenaktive Systeme erforderlich. Redoxaktive langkettige Polyene wie die „Caroviologene“ können als molekulare Drähte für den Elektronentransport durch Membranen betrachtet werden. Push-pull-Polyene haben ausgeprägte nichtlineare optische Eigenschaften. Geordnete tubuläre Stapel geeigneter Makrocyclen in Mesophasen sowie Makrocyclen mit langkettigen Substituenten und funktionellen Gruppen an deren Enden („Chundles“) sind Prototypen von Ionenkanälen. Mit lipophilen Makrocyelen können Langmuir-Blodgett-Filme hergestellt werden, die eine molekulare Erkennung an der Luft-Wasser-Grenzfläche ermöglichen könnten. Die Supramolekulare Chemie war bisher auf mehr oder weniger vorgeformte („präorganisierte“) Rezeptoren für die molekulare Erkennung, Katalyse und Transportprozesse angewiesen. Einen Schritt weiter geht der Entwurf von Systemen, bei denen auf molekularer Ebene eine Selbstorganisation möglich ist und die spontan eine genau definierte supramolekulare Struktur annehmen. Mehrere selbstorganisierende Systeme wurden beschrieben: 1. Helicale Metallkomplexe/doppelsträngige Helicate: Zwei lineare Polybipyridine koordinieren bestimmte Metall-Ionen unter spontaner Bildung einer Doppelhelix. 2. Mesophasen und flüssigkristalline Polymere: Durch molekulare Erkennung entstehen aus komplementären Komponenten supramolekulare Verbände mit entsprechenden makroskopischen Eigenschaften. 3. Geordnete Festkörperstrukturen: Durch molekulare Erkennung kann der Aufbau geordneter Festkörper gesteuert warden. Baut man in Moleküle mit Photo-, Elektro- oder Ionenaktivität Erkennungselemente ein, so eröffnet sich die Perspektive, „programmierte“ molekulare und supramolekulare Systeme herzustellen, die sich selbst  -  gesteuert durch die molekulare Erkennung  -  zu geordneten supramolekularen Funktionseinheiten zusammensetzen. Diese Funktionseinheiten könnten dann selektive Erkennung, Reaktion, Übertragung und Strukturerzeugung bei der Signal- und Informationsverarbeitung auf molekularer Ebene übernehmen.
    Additional Material: 15 Ill.
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  • 7
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 29 (1990), S. 1304-1319 
    ISSN: 0570-0833
    Keywords: Self-assembly ; Information processing ; Molecular information processing ; Molecular recognition ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The selective binding of a substrate by a molecular receptor to form a supramolecular species involves molecular recognition which rests on the molecular information stored in the interacting species. The functions of supermolecules cover recognition, as well as catalysis and transport. In combination with polymolecular organization, they open ways towards molecular and supramolecular devices for information processing and signal generation. The development of such devices requires the design of molecular components performing a given function (e.g., photoactive, electroactive, ionoactive, thermoactive, or chemoactive) and suitable for assembly into an organized array. Light-conversion devices and charge-separation centers have been realized with photoactive cryptates formed by receptors containing photosensitive groups. Eleclroactive and ionoactive devices are required for carrying information via electronic and ionic signals. Redox-active polyolefinic chains, like the “caroviologens”, represent molecular wires for electron transfer through membranes. Push-pull polyolefins possess marked nonlinear optical properties. Tubular mesophases, formed by organized stacking of suitable macro-cyclic components, as well as “chundle”-type structures, based on bundles of chains grafted onto a macrocyclic support, represent approaches to ion channels. Lipophilic macrocyclic units form Langmuir-Blodgett films that may display molecular recognition at the air-water interface. Supramolecular chemistry has relied on more or less preorganized molecular receptors for effecting molecular recognition, catalysis, and transport processes. A step beyond preorganization consists in the design of systems undergoing self-organization, that is, systems capable of spontaneously generating a well-defined supramolecular architecture by self-assembling from their components under a given set of conditions. Several approaches to self-assembling systems have been pursued: the formation of helical metal complexes, the double-stranded helicates, which result from the spontaneous organization of two linear polybipyridine ligands into a double helix by binding of specific metal ions; the generation of mesophases and liquid crystalline polymers of supramolecular nature from complementary components, amounting to macroscopic expression of molecular recognition; the molecular-recognition-directed formation of ordered solid-state structures. Endowing photo-, electro-, and ionoactive components with recognition elements opens perspectives towards the design of programmed molecular and supramolecular systems capable of self-assembly into organized and functional supramolecular devices. Such systems may be able to perform highly selective operations of recognition, reaction, transfer, and structure generation for signal and information processing at the molecular and supramolecular levels.
    Additional Material: 15 Ill.
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  • 9
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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