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

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

Center for Molecular Modeling - J. Romanova

PPV Polymerization via the Gilch Route: Diradical Character of Monomers

Abstract

DOI

Private attachment

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

Conference / event / venue