Center for Molecular Modeling - D. Vanderzande

PPV Polymerization via the Gilch Route: Diradical Character of Monomers

michel — Sun, 17 May 2015 20:16:36 +0000

J.D. Nikolic, S. Wouters, J. Romanova, A. Shimizu, B. Champagne, T. Junkers, D. Vanderzande, D. Van Neck, M. Waroquier, V. Van Speybroeck, S. Catak

Chemistry - A European Journal

21, 19176-19185

2015

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.

DOI

http://dx.doi.org/10.1002/chem.201501900

Private attachment

Chem. Eur. J. 21, 19176-19185 (2015).pdf

Kinetic and Mechanistic Study on p-Quinodimethane Formation in the Sulfinyl Precursor Route for the Polymerization of Poly(p-phenylenevinylene) (PPV)

wim — Tue, 13 Sep 2011 12:01:44 +0000

L. Hermosilla, S. Catak, V. Van Speybroeck, M. Waroquier, J. Vandenbergh, F. Motmans, P. Adriaensens, L. Lutsen, T. Cleij, D. Vanderzande

Macromolecules

43 (18), 7424–7433

2010

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 E2 mechanism is proposed for the p-quinodimethane formation in the sulfinyl precursor route.

DOI

http://dx.doi.org/10.1021/ma1013012

Private attachment

10 macromolecules 43, 7424 hermosilla.pdf

Computational insight into the polymerization of conjugated electroluminescent polymer PPV: Diradical character of monomers and dimers

samuel — Wed, 05 Feb 2020 14:09:32 +0000

J. Durdevic, S. Wouters, J. Romanova, A. Shimizu, B. Champagne, T. Junkers, D. Vanderzande, D. Van Neck, M. Waroquier, V. Van Speybroeck, S. Catak

ISBN/ISSN:0065-7727

Talk

Conference / event / venue

250th ACS National Meeting & Exposition - Division of Catalysis Science and Technology (CATL)

Boston, MA, USA

Sunday, 16 August, 2015 to Thursday, 20 August, 2015

PPV Polymerization via the Gilch Route: Effect of Diradical Character of Monomers and Dimers

catak — Thu, 12 Jun 2014 11:58:28 +0000

J. Durdevic, S. Catak, S. Wouters, B. Champagne, T. Junkers, D. Vanderzande, M. Waroquier, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

Promoting Female excellence in Theoretical and Computational Chemistry II

Oslo, Norway

Friday, 13 June, 2014 to Monday, 16 June, 2014

Abstract (private)

Catak-Saron-poster.pdf

DFT insight into the polymerization mechanism of conjugated electroluminescent polymer PPV

catak — Wed, 23 Oct 2013 13:27:02 +0000

J. Durdevic, S. Catak, A. Shimizu, B. Champagne, T. Junkers, D. Vanderzande, M. Waroquier, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

Structure-property relationships of molecular precursors to organic electronics

Lausanne, Switzerland

Tuesday, 22 October, 2013 to Friday, 25 October, 2013

Abstract (private)

CECAM-Poster Abstract-Saron Catak.pdf

Kinetic and Mechanistic Study on the radical PPV polymerization via the Gilch route including diradical character of different monomers and dimers

wim — Thu, 26 Sep 2013 13:20:30 +0000

J. Durdevic, S. Catak, B. Champagne, T. Junkers, D. Vanderzande, M. Waroquier, V. Van Speybroeck

ISBN/ISSN:

Talk

Conference / event / venue

Annual IAP Meeting

Ghent, Belgium

Wednesday, 18 September, 2013

Conference reference

Annual IAP Meeting (2013)

DFT insight into the polymerization mechanism of conjugated electroluminescent polymer PPV

catak — Wed, 18 Jan 2012 17:05:17 +0000

S. Catak, L. Hermosilla, B. Champagne, D. Vanderzande, M. Waroquier, V. Van Speybroeck

WP2/5

Poster

Conference / event / venue

Belgium Science Policy (Belspo)–Annual Meeting for Interuniversity Attraction Poles (IUAP)

Leuven, Belgium

Monday, 21 November, 2011 to Tuesday, 22 November, 2011

Abstract (private)

2011 IAP WP2_5.pdf

Conference reference

Annual Meeting for Interuniversity Attraction Poles (IUAP) 2011

DFT insight into the mechanism towards the synthesis of the conjugated electroluminescent polymer PPV

wim — Mon, 17 Oct 2011 14:25:00 +0000

L. Hermosilla, V. Van Speybroeck, M. Waroquier, D. Vanderzande

Poster

Conference / event / venue

IAP-PAI P6/27 Annual Meeting

Leuven, Belgium

Monday, 14 December, 2009 to Tuesday, 15 December, 2009