MODELING THE GROWTH AND MOLECULAR-STRUCTURE OF CONDUCTIVE POLYMERS - APPLICATION TO POLY(DIALKOXYBENZENE)S

Citation
Jc. Lacroix et al., MODELING THE GROWTH AND MOLECULAR-STRUCTURE OF CONDUCTIVE POLYMERS - APPLICATION TO POLY(DIALKOXYBENZENE)S, Structural chemistry, 8(3), 1997, pp. 177-188
Citations number
30
Categorie Soggetti
Chemistry
Journal title
ISSN journal
10400400
Volume
8
Issue
3
Year of publication
1997
Pages
177 - 188
Database
ISI
SICI code
1040-0400(1997)8:3<177:MTGAMO>2.0.ZU;2-1
Abstract
A modeling strategy, based on (i) quantum semiempirical calculation of the electronic structure of the successive intermediate oligomers and (ii) evaluation of the activation energy of the successive coupling r eactions by use of the frontier orbital model, has been used to study the growth of a wide set of conductive polymers and is illustrated wit h poly(1,2-dialkoxybenzene) and poly(1,4-dialkoxybenzene) generated by electrochemical oxidation of the corresponding monomer. These monomer s have been chosen because they are known to yield polymers of complet ely different structures. The strategy, which is designed to be as lit tle computer time-consuming as possible, allows us to predict a growth trend in agreement with the structure inferred from spectrochemical e xperiments. In the case of poly(1,2-dialkoxybenzene) it suggests the f ormation of a cyclic tetramer as a byproduct detected in small quantit ies by means of MALDI spectroscopy. This modeling strategy allows one to describe the electronic modifications induced by the growth of a hi ghly conjugated structure. It suggests that oxidation of the successiv e oligomers at high doping level and quinonic deformation are key fact ors for the growth of long and regular polymer structures.