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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/21710

Title: PPV Polymerization through the Gilch Route: Diradical Character of Monomers
Authors: Nikolic, Jelena D.
Wouters, Sebastian
Romanova, Julia
Shimizu, Akihiro
Champagne, Benoit
Junkers, Thomas
Vanderzande, Dirk
Van Neck, Dimitri
Waroquier, Michel
Van Speybroeck, Veronique
Catak, Saron
Issue Date: 2015
Citation: CHEMISTRY-A EUROPEAN JOURNAL, 21 (52), p. 19176-19185
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.
Notes: [Nikolic, Jelena D.; Wouters, Sebastian; Van Neck, Dimitri; Waroquier, Michel; Van Speybroeck, Veronique; Catak, Saron] Univ Ghent, Ctr Mol Modeling, B-9052 Zwijnaarde, Belgium. [Nikolic, Jelena D.] Univ Kragujevac, Fac Sci, Kragujevac 34000, Serbia. [Romanova, Julia; Shimizu, Akihiro; Champagne, Benoit] Univ Namur, Lab Chim Theor, B-5000 Namur, Belgium. [Junkers, Thomas; Vanderzande, Dirk] Hasselt Univ, Inst Mat Res Imo Imomec, B-3500 Hasselt, Belgium. [Catak, Saron] Bogazici Univ, Dept Chem, TR-34342 Istanbul, Turkey. [Junkers, Thomas; Vanderzande, Dirk] IMEC, IMOMEC Ass Lab, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/21710
DOI: 10.1002/chem.201501900
ISI #: 000368282100042
ISSN: 0947-6539
Category: A1
Type: Journal Contribution
Validation: ecoom, 2017
Appears in Collections: Research publications

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