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http://hdl.handle.net/1942/21710
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DC Field | Value | Language |
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dc.contributor.author | Nikolic, Jelena D. | - |
dc.contributor.author | Wouters, Sebastian | - |
dc.contributor.author | Romanova, Julia | - |
dc.contributor.author | Shimizu, Akihiro | - |
dc.contributor.author | Champagne, Benoit | - |
dc.contributor.author | JUNKERS, Tanja | - |
dc.contributor.author | VANDERZANDE, Dirk | - |
dc.contributor.author | Van Neck, Dimitri | - |
dc.contributor.author | Waroquier, Michel | - |
dc.contributor.author | Van Speybroeck, Veronique | - |
dc.contributor.author | Catak, Saron | - |
dc.date.accessioned | 2016-07-12T10:33:46Z | - |
dc.date.available | 2016-07-12T10:33:46Z | - |
dc.date.issued | 2015 | - |
dc.identifier.citation | CHEMISTRY-A EUROPEAN JOURNAL, 21 (52), p. 19176-19185 | - |
dc.identifier.issn | 0947-6539 | - |
dc.identifier.uri | http://hdl.handle.net/1942/21710 | - |
dc.description.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. | - |
dc.description.sponsorship | The authors acknowledge BELSPO in the frame of IAP-PAI P7/05. V.V.S. acknowledges funding from the European Research Council under the European Community's Seventh Framework Program (FP7(2007-2013) ERC grant agreement number 240483). J.R. thanks the F.R.S-FNRS for her postdoctoral fellowship under convention number 1.5133.12. The computational resources and services used in this work were provided by the VSC (Flemish Supercomputer Center), funded by the Research Foundation - Flanders (FWO) and the Flemish Government – department EWI as well as by the Consortium des Equipements de Calcul Intensif (CECI), in particular by the Plateforme Technologique de Calcul Intensif (PTCI) of the University of Namur, funded by the FNRS-FRFC (Convention numbers 2.4.617.07.F and 2.5020.11) and the University of Namur. S.W. acknowledges a Gustave Boel-Sofina postdoctoral fellowship from the King Baudouin Foundation and the Belgian-American Educational Foundation. | - |
dc.language.iso | en | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.rights | © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim | - |
dc.subject.other | density functional calculations; diradicals; polymerization; radicals; reaction mechanisms | - |
dc.subject.other | density functional calculations; diradicals; polymerization; radicals; reaction mechanisms | - |
dc.title | PPV Polymerization through the Gilch Route: Diradical Character of Monomers | - |
dc.type | Journal Contribution | - |
dc.identifier.epage | 19185 | - |
dc.identifier.issue | 52 | - |
dc.identifier.spage | 19176 | - |
dc.identifier.volume | 21 | - |
local.format.pages | 10 | - |
local.bibliographicCitation.jcat | A1 | - |
dc.description.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. | - |
local.publisher.place | WEINHEIM | - |
local.type.refereed | Refereed | - |
local.type.specified | Article | - |
local.type.programme | VSC | - |
dc.identifier.doi | 10.1002/chem.201501900 | - |
dc.identifier.isi | 000368282100042 | - |
item.fulltext | With Fulltext | - |
item.fullcitation | Nikolic, Jelena D.; Wouters, Sebastian; Romanova, Julia; Shimizu, Akihiro; Champagne, Benoit; JUNKERS, Tanja; VANDERZANDE, Dirk; Van Neck, Dimitri; Waroquier, Michel; Van Speybroeck, Veronique & Catak, Saron (2015) PPV Polymerization through the Gilch Route: Diradical Character of Monomers. In: CHEMISTRY-A EUROPEAN JOURNAL, 21 (52), p. 19176-19185. | - |
item.accessRights | Restricted Access | - |
item.validation | ecoom 2017 | - |
item.contributor | Nikolic, Jelena D. | - |
item.contributor | Wouters, Sebastian | - |
item.contributor | Romanova, Julia | - |
item.contributor | Shimizu, Akihiro | - |
item.contributor | Champagne, Benoit | - |
item.contributor | JUNKERS, Tanja | - |
item.contributor | VANDERZANDE, Dirk | - |
item.contributor | Van Neck, Dimitri | - |
item.contributor | Waroquier, Michel | - |
item.contributor | Van Speybroeck, Veronique | - |
item.contributor | Catak, Saron | - |
crisitem.journal.issn | 0947-6539 | - |
crisitem.journal.eissn | 1521-3765 | - |
Appears in Collections: | Research publications |
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nikolic 1.pdf Restricted Access | Published version | 1.13 MB | Adobe PDF | View/Open Request a copy |
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