Ghent University Academic Bibliography

Advanced

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

Laura Hermosilla UGent, Saron Catak UGent, Veronique Van Speybroeck UGent, Michel Waroquier UGent, Joke Vandenbergh, Filip Motmans, Peter Adriaensens, Laurence Lutsen, Thomas Cleij and Dirk Vanderzande (2010) MACROMOLECULES. 43(18). p.7424-7433
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.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
DENSITY-FUNCTIONAL THEORY, FREE-RADICAL POLYMERIZATION, GILCH SYNTHESIS, PROPAGATION RATE, ADJUSTABLE-PARAMETERS, THERMOCHEMICAL KINETICS, SOLVATION MODELS, ADIABATIC CONNECTION, CONTINUUM SOLVENT CALCULATIONS, AB-INITIO
journal title
MACROMOLECULES
Macromolecules
volume
43
issue
18
pages
7424 - 7433
Web of Science type
Article
Web of Science id
000281883000007
JCR category
POLYMER SCIENCE
JCR impact factor
4.837 (2010)
JCR rank
5/78 (2010)
JCR quartile
1 (2010)
ISSN
0024-9297
DOI
10.1021/ma1013012
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1055580
handle
http://hdl.handle.net/1854/LU-1055580
date created
2010-10-08 09:31:07
date last changed
2013-09-17 10:46:41
@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},
}

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.