Chiral poly(3-(3,7-dimethyloctyloxy)thiophene)s were prepared using three different methodologies, rendering polymers with different degrees of regioregularity. In a first attempt, 3alkoxythiophene was polymerized using FeCl 3 , resulting in a highly regioirregular poly(3alkoxythiophene).Secondly, the GRIM methodology was applied, which yielded poly(3alkoxythiophene)s with relatively high, but not perfect, degrees of regioregularity. Finally, an alternative methodology was used, which consisted of the exclusive formation and subsequent 2 polymerization of 2-bromomagnesio-3-(3,7-dimethyloctyloxy)-5-bromothiophene) and which resulted in poly(3-alkoxythiophene)s with (almost) perfect regioregularity. The degrees of regioregularity were evaluated with 1 H NMR, UV-Vis and CD spectroscopy and cyclic voltammetry. These (regioregular) poly(3-alkoxythiophene)s show a very high λ max , indicating very high conjugation lengths. Moreover, the polymers could easily be oxidized and they were stable in both neutral as well as oxidized state.This stability can be correlated with the decrease in oxidation potential. The reproducibility and reversibility of the oxidation was demonstrated by UV-Vis spectroscopy. Finally, the chiral properties of the polymers were investigated with circular dichroism spectroscopy. These experiments demonstrated again the difference in regioregularity of the polymers.

A chiral, regioregular head-to-head-tail-to-tail coupled poly(3-alkoxythiophene) (HH-TT-P3AOT) was prepared by a Stille-coupling reaction. The influence of the substitution pattern on the chiroptical properties of regioregular P3AOTs was investigated by comparing the chiroptical behavior of HH-TT-P3AOT and a chiral HT-P3AOT. The UV-vis and CD spectra of HH-TT-P3AOT display an additional absorption band with corresponding monosignate Cotton effect, which can be ascribed to the supramolecular organization of HH-TT-P3AOT.

SummaryPoly(3-alkoxythiophene)s with different degrees of regioregularity were prepared using three different methodologies. It is shown that their Faraday rotation is highly dependent on the degree of regioregularity. The origin of the differences in regiospecificity of the methodologies is discussed.2

8 new chiral, chromophore-functionalized donor-embedded polybinaphthalenes were prepared and characterized for their (nonlinear) optical properties. The polymers were prepared by direct polymerization using a Stille coupling reaction between a chiral bis(trimethyltin) binaphthalene derivative and diiodo-functionalized chromophores. The use of diiodo-functionalized instead of dibromo-functionalized chromophores resulted in a significant increase of molecular weight, as demonstrated by end-group analysis, GPC and MALDI-TOF experiments. The reaction conditions allowed the use of a great variety of chromophores with different DπA-structures. The typical treelike macromolecular architecture of the polymers is reflected in the behavior of the glass transition temperature and, more clearly, in the nonlinear optical properties. The nonlinear optical response shows a continuous, linear increase in function of chromophore concentration, indicating that the dipolar interactions between the chromophores are eliminated. Moreover, chiral contributions to the nonlinear optical response were observed and mounted 14 % of the highest achiral contribution.

Abstract. A series of chiral, chromophore-functionalized donor-embedded polybinaphthalenes were prepared by a Stille coupling reaction between a diiodo-functionalized chromophore and a 2 bis(trimethyltin) binaphthalene derivative. The optical purity of the chiral binaphthalene monomer was varied and its influence on the conformation of the polymers was investigated. Differential scanning calorimetry (DSC) and second-harmonic generation (SHG) experiments revealed that the mobility of the chromophore in the polymers, prepared from optically impure monomers, is much higher than in that of polymers obtained by polymerization of optically pure monomers. Hyper-Rayleigh scattering (HRS) measurements demonstrated that this difference in mobility is due to a different macromolecular structure.