This article features recent advances in the synthesis of conjugated polymers via a controlled polymerization. These polymerizations typically rely on transition metal catalyzed cross coupling reactions. The mechanisms of the polymerization protocols are discussed in detail. An overview of all possible protocols and all homopolymers that have been investigated is given. Next, the synthesis of copolymers-random, gradient and block copolymers-is reviewed. Another advantage of a controlled polymerization is the possibility to introduce specific functional groups, either at the beginning of each polymer chain by the use of an external initiator, or at the end of the polymer chain using an endcapper. Finally, topologies different from simple linear polymer chains are discussed. This feature article is complementary to other recent review articles on this topic. 1,2

The synthesis of a block copoly(3-alkylthiophene) consisting of two different P3AT blocks equipped with an H-donor and -acceptor functionality is presented. The P3ATs were synthesized using a functionalized Ni-initiator. By a series of postpolymerization reactions, including click chemistry, a H-donor and -acceptor entity were attached to the end of the polymer chains. Evidences for a quantitative functionalization of the polymers were provided by 1 H NMR and MALDI-ToF analyses. Chiral side chains were implemented on one of both blocks, allowing the study of the influence of the H-bond formation on the chiral self-assembly using UV-vis and circular dichroism (CD) spectroscopy.

Fe3O4 nanoparticles decorated with a conjugated polymer is synthesized and the supramolecular organization of the polymer is studied.

The attachment of conjugated polymers (CPs), characterized by their optical and electronic properties and excellent processability, to inorganic nanoparticles (NPs), known for their specialized electronic and photonic properties, has proven to result in unique and promising (hybrid) materials. Although CPs can be functionalized with many different end groups, the process to find a correct match between the desired NP and appropriate functional group on the CP is often tedious and time-consuming. This study aims to solve this problem by investigating the potential of catechol as a universal linker molecule for the synthesis of hybrid CP/NP materials. First, the synthesis of poly­(9,9-di­((S)-3,7-dimethyloctyl)­fluorene) via Suzuki–Miyaura catalyst transfer oxidative polycondensation using an external catechol Pd-initiator is investigated. A chain-growth polymerization without transfer reactions for molar masses up to 28.3 kg mol–1 is established without degradation of the catechol in basic environments. These polymers are subsequently used to graft a variety of NP materials, including magnetic- (Fe3O4), plasmonic- (Au), and oxide-type (SiO2) NPs, proving its potential as a universal linker molecule. In addition, the influence of the catechol group on the supramolecular organization of free polyfluorene is investigated by comparison with the well-known o-tolyl end-capped polyfluorenes. From these results, it can be concluded that the catechol group significantly disrupts the formation of well-defined supramolecular architectures. Finally, as a preliminary study, the supramolecular organization of the hybrid NPs is compared to the free polymer using solvatochromism experiments. The results indicate an absence of chiral response upon fixation of the polymer onto a surface.

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