Molecular self-assembly of 1D infinite polyiodide helices in a phenanthrolinium salt

Abstract

A new linear polymeric polyiodide, catena-poly[tris(1,10-phenanthrolin-1-ium)tris(1,10-phenanthroline)heptaiodide], was prepared by one-step synthesis. Its formation is driven by hydrogen-bond assisted supramolecular assembly in the presence of chromium(III) acetate. Its structure has been characterized by the means of single-crystal X-ray diffraction. To date, this is only one of the few examples of organized linear infinite polyiodides with a known structure. The interplay between the interactions within the hypervalent iodine chain and its supramolecular environment is elucidated. The electrical, thermal, and spectroscopic properties of the studied compound were investigated and associated with the structural features. The infinite character of the polyiodide chain and its similarity to the blue starch–iodine complex has been additionally confirmed by Raman spectroscopy. Despite the apparent structural and spectroscopic similarities with the previously reported 1D polymeric polyiodide, its physical properties, i.e. electrical conductivity and thermal stability, differ significantly. This can be rationalized by the differences in the orbital overlap within the iodine chain, as well as the distinct interactions with the cation.