Expression of Supramolecular Chirality in Block Copoly(thiophene)s

Abstract

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.

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

“…The first all-thiophene-based block copolymer, P3HT-b-poly(3-dodecylthiophene) (P3DDT), was prepared by Iovu et al [22] Since then, a number of related block copolymers with all-polythiophene backbones but different side chains were synthesized. [36,38] Block copolymers with P3HT and poly(2-ethyl-3-hexylthiophene) (P2E3HT) have received particular attention. Ho et al, [39] Zhang et al, [40] and Ohshimitsu and Ueda [41] have synthesized poly(3-hexylthiophene)-block-poly(3-(2-ethylhexyl)thiophene), P3HT-b-P2E3HT, via sequential addition of monomers.…”

Kumada chain-growth polycondensation as a universal method for synthesis of well-defined conjugated polymers

“…In the melt phase, it could assemble into a microphase-separated lamellar structure with two crystalline domains. Polythiophene-based FCBPs with one block carrying functional groups, such as P3RT-b-P3ORT and P3HT-b-P3AET, were prepared for studying supramolecular chirality or postfunctionalization [46,67]. FCBP with naphthalimide moieties in side chains was prepared from P3HT-b-P3AET via "click" chemistry method [46].…”

The Influence of Solubilizing Chain Stereochemistry on Small Molecule Photovoltaics

“…), solubilizing groups emerge as important structural components for study and material/device optimization. Indeed, for both oligomers and polymers, side chain type, length, branching, placement, and stereochemistry have independently been shown to influence thin film morphology, charge carrier mobility, and device performance …”