Flexible Chirality in Self-Assembled N-Annulated Perylenedicarboxamides

Abstract

N-annulated perylenedicarboxamides 1-3 form supramolecular polymers with a strong tendency to aggregate. The bundles of fibers formed generate a spontaneous anisotropy that conditions the chiroptical features of the described molecules in solution; a strong linear dichroism effect accompanies the circular dichroism (CD) outcome. There is no influence of the point chirality existing at the side chains of 1 and 2, and these molecules present the same chiroptical features as achiral 3. Mechanical rotary stirring increases the CD response and the sign of the dichroic signal changes with the stirring direction. Theoretical calculations indicate that the self-assembly of 1-3 in helical columnar stacks generates atropisomers by the restricted rotation of the H-bonded benzamide units. Molecular mechanics/molecular dynamics calculations predict a feasible intrastack stereomutation of the helical aggregates due to the rapid rupture/formation of the amide H-bonds. This oscillating helicity, together with the fact that right- and left-handed helices are predicted to be mostly isoenergetic, justifies the negligible contribution of the molecular chirality embedded in the paraffinic side chains of 1 and 2. The reported CD behavior contributes to shed light on the physical processes promoting flexible macroscopic chirality that, in turn, can be utilized for the spectroscopic visualization of torsional flows generated in a vortex.

Keywords: chirality; circular dichroism; convective flow; helical aggregates; supramolecular polymers.