Planar inorganic five-membered heterocycles with σ + π dual aromaticity in both S 0 and T 1 states.

Cyclic species being aromatic in both the lowest singlet and triplet electronic states (so-called adaptive aromaticity) are scarce. To date, the reported systems have been mostly organometallic heterocycles with the aromaticities in the two states having the same origin of either σ- or π-electron delocalization ( i.e. , adaptive σ or π aromaticity). Herein, an exhaustive density functional theory study was conducted for 90 planar inorganic five-membered heterocycles in the forms of XY 4 and XY 2 Z 2 (X = O or S; Y and Z = N, P, As, Sb or Bi). They all contain 6π electrons and thus should be aromatic and antiaromatic in the lowest singlet and triplet states, respectively, according to classical Hückel's 4 n + 2 and Baird's 4 n π-electron rules. To our surprise, however, several of them ( e.g. , ON 2 As 2 , ON 2 Bi 2 and SAs 2 Sb 2 ) exhibit considerable aromatic characters in both S 0 and T 1 states, as confirmed by multiple aromaticity indices. More interestingly, further analyses reveal that their aromaticities in the two states may unprecedentedly stem from both σ- and π-electron delocalization. Thus, they likely bear unusual adaptive σ + π dual aromaticity. By finding adaptive aromatics in rather simple inorganic unsaturated systems, our work extends this emerging aromaticity concept to the big inorganic world.