Synthesis of stable polymetalated aromatic complexes through metal–macrocycle capsule-triggered cyclization

Abstract

Polymetalated aromatic compounds are of great interest because of their intermediate roles in many organic transformations. However, they are elusive and synthetically challenging. In this study, a dynamic coordination capsule constructed by a flexible macrocycle and silver(I) ions is applied to trigger one-step or cascade cyclization reactions for various alkyne substrates, finally leading to five unprecedented polysilver heteroaromatic intermediates (including indole, quinoline, benzocarbazole and 2,2′-biindole). The acquired heteroaromatic species is doubly charged, particularly at vicinal positions, and each is surrounded by a tetrasilver aggregate. The metal–macrocycle capsule holds a great potential of flexibly adjusting its conformation to adapt different polysilver heteroaromatic species. DFT calculations further reveal that metal-perturbed aromaticity and multi-centered bonding both contribute to stabilization of the polysilver heteroaromatic complexes.