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  • 1
    Electronic Resource
    Electronic Resource
    Molecular complexes between octaethyltetrathiaporphyrin dication and electron donors: A spectroscopic and electrochemical study (1995)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 647-658 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Octaethyltetrathiaporphyrin dication, OTP2+, is electrochemically reduced by two successive electron-transfer processes to OPT0. OPT2+ forms intermolecular complexes with a series of π-donors. The association constants of the resulting complexes are controlled by the oxidation potentials of the π-donors and solvent properties. OTP2+ was incorporated into a Nafion membrane cast on a Pt electrode. Formation of OTP2+-π-donor complexes in the polymer membrane was followed by electrochemical and spectroscopic means. The association constants of the OTP2+-π-donor complexes in the Nafion membrane exhibit lower values than a homogeneous phase owing to the high ionic strength in the polyelectrolyte.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610081004
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  • 2
    Electronic Resource
    Electronic Resource
    Molecular aggregates between octaethyltetrathiaporphyrin dication (OTP2+) and octaethylporphyrin (H2OEP) and its metal complexes (1995)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 659-670 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The octaethyltetrathiaporphyrin dication, OTP2+, forms 1:1 intermolecular donor-acceptor complexes with NiII-, VIVO- and FeIII-octaethylporphyrins. The association constants of the complexes are governed by the oxidation potential of the metallo-octaethylporphyrins and by secondary electrostatic interactions. Octaethylporphyrin, H2OEP, forms intermolecular complexes with OTP2+. Kinetic analyses of the formation of the various complexes revealed the formation of a primary complex exhibiting the stoichiometry (OTP2+)2(H2OEP). This intermolecular complex transforms into a thermodynamically stabilized intermolecular assembly with a stoichiometry corresponding to (OTP2+)4H2OEP. The activation barrier associated with the conversion of the primary complex to the thermodynamically stabilized assembly is Ea = 16·5 kcal mol-1 (1 kcal = 4·184 kJ). The association constant of the complex (OTP2+)2(H2OEP) is K1 = 1·3 × 1010 M-2 and the equilibrium constant between the two coexisting intermolecular complexes (OTP2+)4(H2OEP) and (OTP2+)2(H2OEP) is K2 = 7·4.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610081005
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  • 3
    Electronic Resource
    Electronic Resource
    Effects controlling the conformational selectivity and association parameters of H-bonded assemblies between di- and triaminotriazines and bemegride (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 29-43 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,4,6-Tris(aminocyclohexyl)triazine (1) and 2,4-bis(aminocyclohexyl)-6-methoxytriazine (2) are present in solution in two and three equilibrating conformations, respectively. The activation barrier for interconversion of the conformers 1a ⇌ 1b is 14·55 ± 0·2 kcal mol-1 (1 kcal = 4·184 kJ) and the activation barrier for interconversion of the conformers 2a ⇌ 2b ⇌ 2c is 14·2 ± 0·2 kcal mol-1. The conformational analyses of 1 and 2 were also followed by molecular mechanics calculations. Compounds 1 and 2 form H-bonded intermolecular complexes with bemegride (3). Association of 3 proceeds by selection of a specific conformation of 1 and 2, i.e. 1b and 2a, respectively. The association constants of 3-1b and 3-2a are to Ka = 915 and 450 l mol-1, respectively. Molecular mechanics calculations for the H-bonded intermolecular assemblies support the experimental observations of the selective conformational association.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060106
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  • 4
    Electronic Resource
    Electronic Resource
    Control of the thermal cis to trans isomerizations of azobenzene and thioindigo derivatives by the formation of supramolecular H-bonded assemblies (1995)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 54-62 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,3-Bis(aminocyclohexyl)-6-methoxy-1,3,5-triazine (1a) forms intermolecular H-bonded complexes with 3,3′-diacetyl-cis-azoenzene (4) and 6,6′-diethoxy-cis-thioindigo (5b), (association constants K = 4.9 × 104 and 3.5 × 105 1 mol-1, respectively). The thermal cis→trans isomerization of 4b and 5b to 3,3′-diacetyl-trans-azobenzene (4a), and 6,6′-diethoxy-trans-thioindigo (5a), is inhibited in the intermolecular complex 1a-4b and 1a-5b. Molecular mechanics calculations support the formation of the intermolecular H-bonded complexes between 1a and 4b or 5b.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610080111
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