Aromaticity has been a central concept in chemistry since the discovery of benzene in the 19th century and has impacted the science of delocalized π-electron systems. The aromaticity of conventional aromatic compounds usually originates from electron delocalization through a single ring that consists of π-symmetric orbitals. Although double aromaticity, i.e. aromaticity composed of two circularly delocalized orbitals, has been theoretically predicted for over 20 years, the double aromaticity of a bench-stable compound is not well explored by experiment. Here we report the synthesis and isolation of the dication of hexakis(phenylselenyl)benzene, as well as its double aromaticity based on structural, energetic, and magnetic criteria. In this dication, cyclic σ-symmetric and π-symmetric delocalized orbitals are formally occupied by ten and six electrons, respectively, and the aromaticity thus follows the 4n + 2 (n = 1, 2,…) electron Hückel rule, regardless of the σ-orbital or π-orbital symmetry.

A new tripodal ligand that features three selenium donors, namely the tris(2-seleno-1-mesitylimidazolyl)hydroborato ligand, [Tse^Mes], has been constructed via the reaction of KBH₄ with 1-mesitylimidazole-2-selone; comparison of the IR spectroscopic data of [Tse^Mes]Re(CO)₃ with those of a variety of related LRe(CO)₃ complexes demonstrates that the [Tse^Mes] ligand is more strongly electron donating than Cp, Cp*, [Tp], [Tp^Me₂] and [Tm^Mes] ligands.