University of Surrey

Test tubes in the lab Research in the ATI Dance Research

PPV Polymerization through the Gilch Route: Diradical Character of Monomers.

Nikolić, JD, Wouters, S, Romanova, J, Shimizu, A, Champagne, B, Junkers, T, Vanderzande, D, Van Neck, D, Waroquier, M, Van Speybroeck, V and Catak, S (2015) PPV Polymerization through the Gilch Route: Diradical Character of Monomers. Chemistry, 21 (52). pp. 19176-19185.

Full text not available from this repository.

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.

Item Type: Article
Authors :
NameEmailORCID
Nikolić, JDUNSPECIFIEDUNSPECIFIED
Wouters, SUNSPECIFIEDUNSPECIFIED
Romanova, Jj.romanova@surrey.ac.ukUNSPECIFIED
Shimizu, AUNSPECIFIEDUNSPECIFIED
Champagne, BUNSPECIFIEDUNSPECIFIED
Junkers, TUNSPECIFIEDUNSPECIFIED
Vanderzande, DUNSPECIFIEDUNSPECIFIED
Van Neck, DUNSPECIFIEDUNSPECIFIED
Waroquier, MUNSPECIFIEDUNSPECIFIED
Van Speybroeck, VUNSPECIFIEDUNSPECIFIED
Catak, SUNSPECIFIEDUNSPECIFIED
Date : 21 December 2015
Identification Number : https://doi.org/10.1002/chem.201501900
Uncontrolled Keywords : density functional calculations, diradicals, polymerization, radicals, reaction mechanisms
Related URLs :
Depositing User : Symplectic Elements
Date Deposited : 17 May 2017 13:46
Last Modified : 17 May 2017 13:46
URI: http://epubs.surrey.ac.uk/id/eprint/840279

Actions (login required)

View Item View Item

Downloads

Downloads per month over past year


Information about this web site

© The University of Surrey, Guildford, Surrey, GU2 7XH, United Kingdom.
+44 (0)1483 300800