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Kinetic and mechanistic study on p-quinodimethane formation in the sulfinyl precursor route for the polymerization of poly(p-phenylenevinylene) (PPV)

(2010) MACROMOLECULES. 43(18). p.7424-7433
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
The kinetics of p-quinodimethane formation in the sulfinyl precursor route for the poly(p-phenylenevinylene) (PPV) polymerization was studied using stop-flow UV-vis spectroscopy and theoretical first principle calculations. Different sulfinyl monomers were studied by means of quantitative kinetic experiments regarding the p-quinodimethane formation in 2-butanol. The influence of the solvent, the nature of the aromatic moiety, and the substituents on the phenyl core was analyzed by means of qualitative experiments. Quantitative measurements, using pseudo-first-order reaction conditions, were performed in order to assess the effect of the polarizer and the leaving group on the reaction rates. To obtain additional fundamental insight into the pathway leading to p-quinodimethane formation, density functional theory calculations were performed and subsequent reaction rate coefficients were determined from a theoretical point of view, enabling a profound comparison with experiment. From all these data, an E-2 mechanism is proposed for the p-quinodimethane formation in the sulfinyl precursor route.
Keywords
DENSITY-FUNCTIONAL THEORY, FREE-RADICAL POLYMERIZATION, GILCH SYNTHESIS, PROPAGATION RATE, ADJUSTABLE-PARAMETERS, THERMOCHEMICAL KINETICS, SOLVATION MODELS, ADIABATIC CONNECTION, CONTINUUM SOLVENT CALCULATIONS, AB-INITIO

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Citation

Please use this url to cite or link to this publication:

Chicago
Hermosilla, Laura, Saron Catak, Veronique Van Speybroeck, Michel Waroquier, Joke Vandenbergh, Filip Motmans, Peter Adriaensens, Laurence Lutsen, Thomas Cleij, and Dirk Vanderzande. 2010. “Kinetic and Mechanistic Study on P-quinodimethane Formation in the Sulfinyl Precursor Route for the Polymerization of Poly(p-phenylenevinylene) (PPV).” Macromolecules 43 (18): 7424–7433.
APA
Hermosilla, L., Catak, S., Van Speybroeck, V., Waroquier, M., Vandenbergh, J., Motmans, F., Adriaensens, P., et al. (2010). Kinetic and mechanistic study on p-quinodimethane formation in the sulfinyl precursor route for the polymerization of poly(p-phenylenevinylene) (PPV). MACROMOLECULES, 43(18), 7424–7433.
Vancouver
1.
Hermosilla L, Catak S, Van Speybroeck V, Waroquier M, Vandenbergh J, Motmans F, et al. Kinetic and mechanistic study on p-quinodimethane formation in the sulfinyl precursor route for the polymerization of poly(p-phenylenevinylene) (PPV). MACROMOLECULES. 2010;43(18):7424–33.
MLA
Hermosilla, Laura, Saron Catak, Veronique Van Speybroeck, et al. “Kinetic and Mechanistic Study on P-quinodimethane Formation in the Sulfinyl Precursor Route for the Polymerization of Poly(p-phenylenevinylene) (PPV).” MACROMOLECULES 43.18 (2010): 7424–7433. Print.
@article{1055580,
  abstract     = {The kinetics of p-quinodimethane formation in the sulfinyl precursor route for the poly(p-phenylenevinylene) (PPV) polymerization was studied using stop-flow UV-vis spectroscopy and theoretical first principle calculations. Different sulfinyl monomers were studied by means of quantitative kinetic experiments regarding the p-quinodimethane formation in 2-butanol. The influence of the solvent, the nature of the aromatic moiety, and the substituents on the phenyl core was analyzed by means of qualitative experiments. Quantitative measurements, using pseudo-first-order reaction conditions, were performed in order to assess the effect of the polarizer and the leaving group on the reaction rates. To obtain additional fundamental insight into the pathway leading to p-quinodimethane formation, density functional theory calculations were performed and subsequent reaction rate coefficients were determined from a theoretical point of view, enabling a profound comparison with experiment. From all these data, an E-2 mechanism is proposed for the p-quinodimethane formation in the sulfinyl precursor route.},
  author       = {Hermosilla, Laura and Catak, Saron and Van Speybroeck, Veronique and Waroquier, Michel and Vandenbergh, Joke and Motmans, Filip and Adriaensens, Peter and Lutsen, Laurence and Cleij, Thomas and Vanderzande, Dirk},
  issn         = {0024-9297},
  journal      = {MACROMOLECULES},
  keyword      = {DENSITY-FUNCTIONAL THEORY,FREE-RADICAL POLYMERIZATION,GILCH SYNTHESIS,PROPAGATION RATE,ADJUSTABLE-PARAMETERS,THERMOCHEMICAL KINETICS,SOLVATION MODELS,ADIABATIC CONNECTION,CONTINUUM SOLVENT CALCULATIONS,AB-INITIO},
  language     = {eng},
  number       = {18},
  pages        = {7424--7433},
  title        = {Kinetic and mechanistic study on p-quinodimethane formation in the sulfinyl precursor route for the polymerization of poly(p-phenylenevinylene) (PPV)},
  url          = {http://dx.doi.org/10.1021/ma1013012},
  volume       = {43},
  year         = {2010},
}

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