Aromaticity in Fully π-Conjugated Multicyclic Macrocycles.

Abstract

The research on aromaticity has mainly focused on monocyclic [n]annulene-like systems or polycyclic aromatic hydrocarbons. For fully π-conjugated multicyclic macrocycles (MMCs), the electronic coupling between the individual constitutional macrocycles would lead to unique electronic structures and aromaticity. The studies on MMCs, however, are quite limited, presumably due to the great challenges to design and synthesize a fully π-conjugated MMC molecule. Herein, we report the facile synthesis of two MMCs (2TMC and 3TMC) in which two and three thiophene-based macrocycles are fused together by employing both intramolecular and intermolecular Yamamoto coupling reactions of a properly designed precursor (7). The monocyclic macrocycle (1TMC) was also synthesized as a model compound. The geometry, aromaticity, and electronic properties of these macrocycles at different oxidation states were investigated by X-ray crystallographic analysis, NMR, and theoretical calculations, which disclosed how the constitutional macrocycles interplay with each other and lead to unique aromatic/antiaromatic character. This study provides new insights into the complex aromaticity in MMC systems.