DFT Study of 1,4-Diazonium-3,6-diolates: Monocyclic Representatives of Unexplored Semi-Conjugated Heterocyclic Mesomeric Betaines.

Compared to the well-known conjugated (1,3-dipolar) and cross-conjugated (1,4-dipolar) heterocyclic mesomeric betaines (HMBs), semi-conjugated HMBs are unexplored and almost unknown. The three discrete classes of HMB are defined by the connectivity between their ring 2π heteroatoms and the odd-conjugated fragments that complete the ring. A single example of a stable, fully-characterized semi-conjugate HMB has been reported. This study employs the density functional theory (DFT) methodology to investigate the properties of a series of six-membered semi-conjugated HMBs. The electronic character of ring substituents is found to significantly influence the structure and electronic properties of the ring. The aromaticity measured by HOMA and NICS(1) indices is increased by π-electron-donating substituents whereas π-electron-withdrawing substituents decrease the calculated aromatic character and ultimately lead to non-planar boat or chair structures. A notable property of all derivatives is the small energy gap between their frontier orbitals.