The Baird’s rule has been applied to a large scope of organic molecular systems for rationalizing the aromaticity reversal in the lowest-lying triplet state. In this study, we demonstrate that the Baird’s rule can be also extended to all-metal systems with σ- and π-aromaticity.

https://pubs.rsc.org/en/Content/ArticleLanding/2020/CC/D0CC05586G#!divAbstract

Based on Hückel’s and Baird’s rules, species are aromatic either in the lowest singlet state (S0) or the lowest triplet state (T1) only. Thus, species with adaptive aromaticity (with aromaticity in both the S0 and T1 states) is particularly rare. On the other hand, σ-aromaticity in the T1 state has been underdeveloped, let alone adaptive σ-aromaticity. Herein, via various aromaticity indices including NICS, ACID and EDDB, we demonstrate adaptive s-aromaticity in an unsaturated three-membered ring, which is a traditional area dominated by π-aromaticity.

Aromaticity is a fundamental chemical concept of ever-increasing diversity. According to Hückel’s and Baird’s rules, cyclic conjugated species with 4n+2 π-electrons are aromatic in the singlet electronic ground state (S0) and antiaromatic in the lowest triplet state (T1), and vice-versa. Thus, species with aromaticity in both states have not yet been reported.

Aromaticity, one of the central topics in chemistry, has attracted continuing interest of both experimentalists and theoreticians.