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PPV polymerization through the Gilch route: diradical character of monomers

(2015) CHEMISTRY-A EUROPEAN JOURNAL. 21(52). p.19176-19185
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Abstract
Despite various studies on the polymerization of poly(p-phenylene vinylene) (PPV) through different precursor routes, detailed mechanistic knowledge on the individual reaction steps and intermediates is still incomplete. The present study aims to gain more insight into the radical polymerization of PPV through the Gilch route. The initial steps of the polymerization involve the formation of a p-quinodimethane intermediate, which spontaneously self-initiates through a dimerization process leading to the formation of diradical species; chain propagation ensues on both sides of the diradical or chain termination occurs by the formation of side products, such as [2.2]paracyclophanes. Furthermore, different p-quinodimethane systems were assessed with respect to the size of their aromatic core as well as the presence of heteroatoms in/on the conjugated system. The nature of the aromatic core and the specific substituents alter the electronic structure of the p-quinodimethane monomers, affecting the mechanism of polymerization. The diradical character of the monomers has been investigated with several advanced methodologies, such as spin-projected UHF, CASSCF, CASPT2, and DMRG calculations. It was shown that larger aromatic cores led to a higher diradical character in the monomers, which in turn is proposed to cause rapid initiation.
Keywords
DENSITY FUNCTIONALS, CONJUGATED POLYMERS, ELECTRONIC-STRUCTURE, POLY(P-PHENYLENE VINYLENE), TRANSITION-METAL DIMERS, INITIO QUANTUM-CHEMISTRY, MAIN-GROUP THERMOCHEMISTRY, SULFINYL PRECURSOR ROUTE, MATRIX RENORMALIZATION-GROUP, NONCOVALENT INTERACTIONS, ELECTRONIC-STRUCTURE, DENSITY FUNCTIONALS, CONJUGATED POLYMERS

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Citation

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Chicago
Nikolic, JD, Sebastian Wouters, J Romanova, A Shimizu, B Champagne, T Junkers, D Vanderzande, et al. 2015. “PPV Polymerization Through the Gilch Route: Diradical Character of Monomers.” Chemistry-a European Journal 21 (52): 19176–19185.
APA
Nikolic, J., Wouters, S., Romanova, J., Shimizu, A., Champagne, B., Junkers, T., Vanderzande, D., et al. (2015). PPV polymerization through the Gilch route: diradical character of monomers. CHEMISTRY-A EUROPEAN JOURNAL, 21(52), 19176–19185.
Vancouver
1.
Nikolic J, Wouters S, Romanova J, Shimizu A, Champagne B, Junkers T, et al. PPV polymerization through the Gilch route: diradical character of monomers. CHEMISTRY-A EUROPEAN JOURNAL. WEINHEIM: WILEY-V C H VERLAG GMBH; 2015;21(52):19176–85.
MLA
Nikolic, JD et al. “PPV Polymerization Through the Gilch Route: Diradical Character of Monomers.” CHEMISTRY-A EUROPEAN JOURNAL 21.52 (2015): 19176–19185. Print.
@article{7083010,
  abstract     = {Despite various studies on the polymerization of poly(p-phenylene vinylene) (PPV) through different precursor routes, detailed mechanistic knowledge on the individual reaction steps and intermediates is still incomplete. The present study aims to gain more insight into the radical polymerization of PPV through the Gilch route. The initial steps of the polymerization involve the formation of a p-quinodimethane intermediate, which spontaneously self-initiates through a dimerization process leading to the formation of diradical species; chain propagation ensues on both sides of the diradical or chain termination occurs by the formation of side products, such as [2.2]paracyclophanes. Furthermore, different p-quinodimethane systems were assessed with respect to the size of their aromatic core as well as the presence of heteroatoms in/on the conjugated system. The nature of the aromatic core and the specific substituents alter the electronic structure of the p-quinodimethane monomers, affecting the mechanism of polymerization. The diradical character of the monomers has been investigated with several advanced methodologies, such as spin-projected UHF, CASSCF, CASPT2, and DMRG calculations. It was shown that larger aromatic cores led to a higher diradical character in the monomers, which in turn is proposed to cause rapid initiation.},
  author       = {Nikolic, JD and Wouters, Sebastian and Romanova, J and Shimizu, A and Champagne, B and Junkers, T and Vanderzande, D and Van Neck, Dimitri and Waroquier, Michel and Van Speybroeck, Veronique and Catak, Saron},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keywords     = {DENSITY FUNCTIONALS,CONJUGATED POLYMERS,ELECTRONIC-STRUCTURE,POLY(P-PHENYLENE VINYLENE),TRANSITION-METAL DIMERS,INITIO QUANTUM-CHEMISTRY,MAIN-GROUP THERMOCHEMISTRY,SULFINYL PRECURSOR ROUTE,MATRIX RENORMALIZATION-GROUP,NONCOVALENT INTERACTIONS,ELECTRONIC-STRUCTURE,DENSITY FUNCTIONALS,CONJUGATED POLYMERS},
  language     = {eng},
  number       = {52},
  pages        = {19176--19185},
  publisher    = {WILEY-V C H VERLAG GMBH},
  title        = {PPV polymerization through the Gilch route: diradical character of monomers},
  url          = {http://dx.doi.org/10.1002/chem.201501900},
  volume       = {21},
  year         = {2015},
}

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