Abstract

Although aromaticity has been observed in inorganic and all-metal species, the concept of antiaromaticity has not been extended beyond organic molecules. Here, we present theoretical and experimental evidence that the 6 pi-electron tetrapnictogen dianions in Na(+)Pn(4)(2-) (Pn = P, As, Sb) undergo a transition from being aromatic to antiaromatic upon electron detachment, yielding the first inorganic antiaromatic Na(+)Pn(4)(-) molecules. Two types of antiaromatic structures were characterized, the conventional rectangular species and a new peculiar quasiplanar rhombus species. Aromaticity and antiaromaticity in the tetrapnictogen molecules were derived from molecular orbital analyses and verified by experimental photodetachment spectra of Na(+)Pn(4)(2-). On the basis of our findings for the tetrapnictogen clusters, we predicted computationally that the organic C4H4- anion also possesses two antiaromatic structures: rectangular and rhombus. Moreover, only the rhombus antiaromatic minimum was found for the radical NC3H4, thus extending the peculiar rhombus antiaromatic structure first uncovered in inorganic clusters into organic chemistry.