Inversion Triggered by Protonation-A Rubyrin with Embedded α,β'-Pyridine Moieties

Abstract

Incorporation of α,β'-pyridine into a [26]hexaphyrin(1.1.0.1.1.0) frame resulted in formation of 29,33-diaza-A,D-di-p-benzi[26]hexaphyrin (A,D-di-p-pyrirubyrin), which acquires a strictly planar conformation with two nitrogen pyridine atoms directed to the center of the macrocyclic core. The mode of α,β'-pyridine incorporation results in efficient 26-electron π-conjugation, as shown by the clear spectroscopic and structural aromatic features. The formation of the trication and tetracation through protonation is accompanied by a conformational flip of one or two pyridinium moieties to result in N-confused or doubly N-confused conformers of the original macrocyclic frame.

Keywords: expanded porphyrins; porphyrinoids; protonation; pyridine; ring inversion.