Three-Dimensional Fully π-Conjugated Macrocycles: When 3D-Aromatic and When 2D-Aromatic-in-3D?

Abstract

Several fully π-conjugated macrocycles with puckered or cage-type structures were recently found to exhibit aromatic character according to both experiments and computations. We examine their electronic structures and put them in relation to 3D-aromatic molecules ( e.g., closo-boranes) and to 2D-aromatic polycyclic aromatic hydrocarbons. Using qualitative theory combined with quantum chemical calculations, we find that the macrocycles explored hitherto should be described as 2D-aromatic with three-dimensional molecular structures (abbr. 2D-aromatic-in-3D) and not as truly 3D-aromatic. 3D-aromatic molecules have highly symmetric structures (or nearly so), leading to (at least) triply degenerate molecular orbitals, and for tetrahedral or octahedral molecules, an aromatic closed-shell electronic structure with 6 n + 2 electrons. Conversely, 2D-aromatic-in-3D structures exhibit aromaticity that results from the fulfillment of Hückel’s 4 n + 2 rule for each macrocyclic path, yet their π-electron counts are coincidentally 6 n + 2 numbers for macrocycles with three tethers of equal lengths. It is notable that 2D-aromatic-in-3D macrocyclic cages can be aromatic with tethers of different lengths, i.e., with π-electron counts different from 6 n + 2, and they are related to naphthalene. Finally, we identify tetrahedral and cubic π-conjugated molecules that fulfill the 6 n + 2 rule and exhibit significant electron delocalization. Yet, their properties resemble those of analogous compounds with electron counts that differ from 6 n + 2. Thus, despite the fact that these molecules show substantial π-electron delocalization, they cannot be classified as true 3D-aromatics.