Triplet-State Structures, Energies, and Antiaromaticity of BN Analogues of Benzene and Their Benzo-Fused Derivatives

It is well known that benzene is aromatic in the ground state (the Hückel's rule) and antiaromatic in the first triplet (T1) excited state (the Baird's rule). Whereas its BN analogues, the three isomeric dihydro-azaborines, have been shown to have various degrees of aromaticity in their ground state, almost no data are available for their T1 states. Thus, the purpose of this work is to theoretically [B3LYP/6-311+G(d,p)] predict structures, energies, and antiaromaticity of T1 dihydro-azaborines and some benzo-fused derivatives. Conclusions are based on spin density analysis, isogyric and hydrogenation reactions, HOMA, NICS, and ACID calculations. The results suggest that singlet-triplet energy gaps, antiaromaticity, and related excited-state properties of benzene, naphthalene, and anthracene could be tuned and controlled by the BN substitution pattern. While all studied compounds remain (nearly) planar upon excitation, the spin density distribution in T1 1,4-dihydro-azaborine induces a conformational change by which the two co-planar C-H bonds in the ground state become perpendicular to each other in the excited state. This predicted change in geometry could be of interest for the design of new photomechanical materials. Excitation of B-CN/N-NH2 1,4-azaborine would have a few effects: Intramolecular charge transfer, aromaticity reversal, rotation, and stereoelectronic Umpolung of the amino group.