Self-assembly of p-phenylenevinylene oligomers

POLY 436

Christophe Grenier, c.grenier@tue.nl, Department of Chemical Engineering and Chemistry, University of Eindhoven, PO Box 513, Eindhoven, 5600MB, Netherlands
Recently, our research group studied in details the self-assembly of (2S)-methylbutyl substituted bis(alkoxy)-p-phenylenevinylene oligomers (OPVs) terminated with a tridodecyloxybenzene moiety on one end and either a diaminotrizaine (OPVnT) or a ureido-s-triazine (OPVnUT) hydrogen-bonding unit on the other end. We demonstrated that the self-assembly proceeds through a cooperative mechanism, with nucleation followed by elongation of the OPV fibers. In this contribution, we investigate further the self-assembly mechanism by looking at the chiral amplification effect. To carry out this study, OPV4T and OPV4UT with 2R-methylbutyl, racemic 2-methylbutyl and achiral butyl side chains were synthesized. Enantiomerically pure intermediate 2R-methylbutanol was obtained via a powerful and versatile asymmetric synthesis using a chiral oxazolidinone as chiral auxiliary. The amplification of chirality in the OPV stacks has been investigated with sergeant-and-soldier and majority rule experiments. The crucial role of the solvent in the self-assembly is revealed by the odd-even solvent effect and chiral solvation. Achiral OPVs were found to form more stable stacks and shows remarkable chirality induction with chiral guest molecules.