[2.2]Paracyclophane (pCp) is a molecule of historic intrigue due to its rare structural, chemical, physical, and optical properties. Although pCp has fascinated researchers for decades, it has been virtually unexplored in supramolecular constructs. In this context, we have recently developed a novel self-assembling pCp derivative, pCp-4,7,12,15-tetracarboxamide ((±)-pCpTA). The positioning of the carboxamide groups are pivotal in this molecular design, as they uniquely enforce transannular (intramolecular) hydrogen bonds and subsequently pre-align the exterior amido atoms for intermolecular hydrogen bond formation in the co-facial π-stacking direction. As observed in the solid-state crystal structure, propagation produces π-stacked pCp nanorods stabilized by hydrogen bonds helically “laced” around the perimeter of the elongated supramolecular structure. The chirality of the assembly is dictated by the planar chirality of the monomer (Rp- or Sp-pCpTA), and arises from the stereospecific self-recognition capabilities of (±)-pCpTA. Furthermore, this assembly persists in solution where it gives rise to characteristic properties of supramolecular polymers.

Chiral self-recognition and supramolecular polymerization of [2.2]paracyclophane

254th National Meeting (2017)

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