Coordination-Driven Folding in Multi-ZnII -Porphyrin Arrays Constructed on a Pillar[5]arene Scaffold

Abstract

Pillar[5]arene derivatives bearing peripheral porphyrin subunits have been efficiently prepared from a deca-azide pillar[5]arene building block (17) and Zn^II -porphyrin derivatives bearing a terminal alkyne function (9 and 16). For the resulting deca-Zn^II -porphyrin arrays (18 and 20), variable temperature NMR studies revealed an intramolecular complexation of the peripheral Zn^II -porphyrin moieties by 1,2,3-triazole subunits. As a result, the molecules adopt a folded conformation. This was further confirmed by UV/Vis spectroscopy and cyclic voltammetry. In addition, we have also demonstrated that the coordination-driven unfolding of 18 and 20 can be controlled by an external chemical stimulus. Specifically, addition of an imidazole derivative (22) to solution of 18 or 20 breaks the intramolecular coordination at the origin of the folding. The resulting molecular motions triggered by the addition of the imidazole ligand mimic the blooming of a flower.

Keywords: CuAAC; molecular folding; molecular machine; pillararene; porphyrin.