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
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.