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  • 1
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: It is demonstrated that the microscopic mechanism of the photorefractive (PR) effect in organic composites with low glass transition temperatures involves the formation of refractive index gratings through a space-charge field-modulated Kerr effect. A tensorial formulation of the macroscopic aspects of the PR Kerr effect and its microscopic interpretation is presented. The second-order dipole orientation term containing the anisotropy of the first-order optical polarizability α(−ω;ω) is shown to yield the dominant contribution to the Kerr susceptibility χ(3)(−ω;ω,0,0). A class of special chromophores having negligible second-order polarizabilities β(−ω;ω,0) and large dipole moments μ has been identified in order to optimize this term. These chromophores are not subject to the efficiency-transparency tradeoff typically encountered with second-order nonlinear optical (NLO) chromophores, providing highly transparent materials with large PR Kerr response. Contrary to previous approaches in this field, the best-performing PR polymers are then expected to employ chromophores that would be useless for second- order applications (negligible β). We report PR of the material 30% 2,6-di-n-propyl-4H-pyran-4-ylidenemalononitrile (DPDCP): 15% N,N′-bis(3-methylphenyl)- N,N′-bis(phenyl)benzidine (TPD):55% poly(methyl methacrylate) (PMMA):0.3% C60 as an illustration of this principle. A 100 μm thick film of this material exhibits a steady-state diffraction efficiency of η=25% and net two-beam coupling of Γ=50 cm−1 at a bias field of 100 V/μm and a wavelength of 676 nm. The macroscopic Kerr susceptibility of the material is related to molecular electronic properties of the chromophore DPDCP which were independently determined by experiments in solution and by quantum chemical calculations. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2397-2401 
    ISSN: 0009-2940
    Keywords: Wittig reaction ; Rapid injection NMR ; Dynamic NMR ; Oxaphosphetanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The course of the Wittig reaction was investigated by rapid injection NMR spectroscopy. Rate constants for the formation of oxaphosphetanes were determined. A new dynamic equilibrium of oxaphosphetanes was observed for the first time. The solvent and substituent dependence of the new effect was investigated. By labeling various oxaphosphetanes with 13C and 17O the lithium salt dependence of the new equilibrium was shown. A lithium adduct of oxaphosphetanes under these conditions is proposed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1183-1186 
    ISSN: 0009-2940
    Keywords: Phenyllithium ; Solid-state NMR ; Chemical shift anisotropy ; Calculations, IGLO ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenyllithium was labeled with 6Li and 13C at the ipso carbon atom, and the tetramer was measured by solid-state NMR. The chemical shift tensor data were obtained by a moment analysis of the spinning side bands and were compared with the results obtained by calculations with the IGLO method. Although no splitting by dipolar spin coupling to 6Li was found the very good agreement between IGLO predictions and experimental results allowed alignment of the tensor axis to the molecular frame and interpretation of the data. The large deshielding of the isotropic chemical shift is mainly due to a decrease of the ΔE term in s̰.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1625-1627 
    ISSN: 1434-193X
    Keywords: Ozonolysis ; Mechanism ; 17O NMR ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of ozonolysis was revisited with the use of 17O-NMR spectroscopy. In a crossover experiment with 17O-labelled benzaldehyde and the ozonides of styrene and ethylidenecyclohexane it was shown that only the ether bridge of the secondary ozonides is carrying the 17O label. This is contrary to results reported earlier and confirms the Criegee mechanism.
    Type of Medium: Electronic Resource
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