Synthesis and Supramolecular Organization of Regioregular Polythiophene Block Oligomers

Sébastien Clément (1, 2) , Franck Meyer (1) , Julien de Winter (3) , Olivier Coulembier (1) , Christophe M. L. Vande Velde (4) , Matthias Zeller (5) , Pascal Gerbaux (6) , J.-Y. Balandier (2) , S. Sergeyev (2) , Roberto Lazzaroni (7) , Philippe Dubois (1) , Yves Geerts (2)

1 SMPC - Laboratoire de Chimie des Matériaux et Polymères
2 Laboratoire de Chimie des Polymères
3 Laboratoire de Chimie Organique
4 Department of Applied Science
5 Department of chemistry
6 Laboratoire de Chimie Organique
7 Laboratory for Chemistry of Novel Materials

The self-assembly of functional polythiophenes was studied by a bottom-up approach “from molecule to polymer”. The synthesis and the X-ray structure of 2,5-dibromo-3-styryl and 3-2',3',4',5',6'-pentafluorostyryl-thiophenes revealed a supramolecular arrangement controlled by π-π interactions between the aromatic rings. A [2+2] photocyclization reaction in the solid state of (E)-1-2',5'-dibromo-3'-thienyl-2-pentafluorophenylethene triggers the formation of a rare cycloadduct composed by thiophene rings. The X-ray analysis confirmed its rctt stereochemistry. The synthesis of P3HT-b-P3ST and P3HT-b-P3STF block oligomers was achieved by a GRIM method in good yields. An indirect proof of well-defined nanostructured organization was provided by the partial photocyclization of pendant styryl moieties under UV-irradiation.

Domaines: Chimie organique

Sébastien Clément, Franck Meyer, Julien de Winter, Olivier Coulembier, Christophe M. L. Vande Velde, et al.. Synthesis and Supramolecular Organization of Regioregular Polythiophene Block Oligomers. Journal of Organic Chemistry, 2010, 75, pp.1561. ⟨10.1021/jo902490m⟩. ⟨hal-00475261⟩