Folding of a Dynamic Macrocyclic System to Stabilize its Cation Radical State

Abstract

A precise design of unsaturated systems remains an important factor that determines the quality of formed products based on a specific spatial orientation, but also defining the available -electron density open for postsynthetic modulation via a redox change. Three strictly defined reagents showing a different degree of flexibility, but also introducing two mutual orientations of reacting ends (parallel and obtuse) determine the quality of formed products obtained via an intramolecular or an intermolecular reaction. The redox activated transformation of mono- and double-looped systems results in a dissimilar oxidation state of a strongly pi-conjugated dication (2 electron process) or a cation-radical (1 electron process) derived from the difference in dynamic of the skeleton documented for monomer and dimer, respectively.