Coaxial Helices in Chiral Supramolecular Aggregates from Highly Hindered Chiral Allenes

Chiral allenes self-assembly following a cooperative mechanism into a supramolecular chiral aggregate consisting of two coaxial helices: the internal helix described by the allene stack and the external helix which consist in a 4-helix described by the four allene substituents. More precisely, this supramolecular aggregate possesses six axially chiral elements within its structure-the allene, the allene stack (internal helix) and the stacks of the four allene substituents (external 4-helix)-. Interestingly, slight variations in the magnitude of the tilting degree while keeping its P- or M- orientation (internal helix) can vary the orientation of the 4-axial motifs at the external helix. Thus, while (P)-1 produces a supramolecular helix with a Theta ca. 15 degrees (P-int) and a M-1/P-2/M-1'/P-2' orientation of the four axial motifs at the periphery, (P)-2 produces a supramolecular helix with a Theta ca. 23 degrees (P-int) and a P-1/P-2/P-1'/P-2' orientation of the four axial motifs at the external helix. As a result, the ECD spectra and the AFM images of the (P)-1 and (P)-2 supramolecular aggregates dominated by the 1 and 1' substituents of the chiral allene indicate opposite handedness although the chirality of the building block and the orientation of the allene stack are the same