A. Shimizu

PPV Polymerization via the Gilch Route: Diradical Character of Monomers

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
A1

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.

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

ISBN/ISSN:0065-7727
Talk

Conference / event / venue 

250th ACS National Meeting & Exposition - Division of Catalysis Science and Technology (CATL)
Boston, MA, USA
zondag, 16 augustus, 2015 t/m donderdag, 20 augustus, 2015

DFT insight into the polymerization mechanism of conjugated electroluminescent polymer PPV

ISBN/ISSN:
Poster

Conference / event / venue 

Structure-property relationships of molecular precursors to organic electronics
Lausanne, Switzerland
dinsdag, 22 oktober, 2013 t/m vrijdag, 25 oktober, 2013
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