Three block copolymers, P3AT(S*)-b-P3AOT, P3AT(R*)-b-P3AOT(S*), and P3AT(S*)-b-P3AOT(S*), composed of an alkyl-and an alkoxy-substituted poly(thiophene) block, were synthesized using the living chain-growth polymerization of poly(3-alkylthiophene)s. One or both of the blocks are equipped with a chiral side chain. The formation of the block copolymers was confirmed by GPC and 1 H NMR experiments. UV-vis, circular dichroism, and emission spectroscopy were used to study the conformational and supramolecular behavior of these block copolymers in solution. This revealed that the block aggregating first upon addition of nonsolvent has a major influence on the stacking and the chiroptical behavior of the other block.

The polymerization of PPV via the sulfinyl precursor route has been investigated with respect to its mechanism. When polymerized in sec-butanol, a purely radical polymerization mechanism is observed as in most precursor polymerization routes. Accordingly, an increase in the reaction temperature induced an increase in the overall yield alongside with a reduction of the average molecular weight of the polymer. Upon changing the monomer concentration in solution before addition of the base NatBuO, an increase in molecular weight is observed, signifying that the polymerization is faster than the mixing of the two reaction components. When changing the solvent to NMP, a competition of anionic and radical polymerization has been established while in THF an anionic polymerization mechanism occurs exclusively. To prevent termination reactions, LDA and LHMDS were introduced as base whereby LHMDS shows less propensity to initiate anionic chain growth due to higher steric hindrance. With polymerizations in presence of the radical quencher TEMPO, the anionic polymerization mechanism could unambiguously be proven.

The anionic polymerization of PPV via the sulfinyl precursor route is further investigated. When LHMDS is employed as the base to form the actively propagating quinodimethane system and THF as the solvent, anionic polymerizations can be observed. With the use of tert- butyl-substituted anionic initiators, specific functional groups can be built in the polymer chain and the chain length can be efficiently controlled, which is demonstrated here for the first time. With introduction of branched side chains on the aromatic core, soluble conjugated PPV material can be obtained with molecular weights in the range of 5000-16,000 g mol(-1).

Via CBr4-mediation bromine functional MDMO-PPVs with controlled molecular weight were obtained and chain extended in further ATRP reactions.

The initiator efficiency in PPV polymerization was tested and PPV-b-(P-tBuA) block copolymers were synthesized. Via hydrolysis amphiphilic materials undergoing micelle formation were obtained.