A Fully Conjugated Planar Heterocyclic [9]Circulene

Abstract

Fully aromatic [n]circulenes have only been known to encompass up to eight aromatic rings (n = 8), with no reports of endeavors in the synthesis of higher-order analogues (n > 8). Herein we present the first [9]circulene, formally a diazatrioxa[9]circulene, along with a tetrahydro-diazatetraoxa[10]circulene. The key transformation, for construction of the macrocyclic framework, is a simple high-yielding dimerizing condensation between 3,6-dihydroxycarbazole and glyoxal. Single crystal X-ray analysis reveals the [9]circulene to be perfectly planar and containing elongated benzene rings, which is induced by strain to accommodate planarity. Alternating bond lengths in the solid state indicate contribution from a [9]radialene resonance structure in the [9]circulene π-system. The central nonaromatic rings of both circulenes have paratropic ring currents, as evident by nucleus independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations, which can be attributed to induced paratropicity from the surrounding aromatic rings.