p‐Benzyne Derivatives that Have Exceptionally Small Singlet—Triplet Gaps and Even a Triplet Ground State.

TLDR: In this paper, the role of substituent rotation on the energy difference between the two nominally singly occupied orbitals (S and A) was investigated and the energy of the A radical orbital was found to be much more sensitive to perturbations within the σ C−C framework than the S MO.

Abstract: In an effort to find a p-benzyne (1,4-didehydrobenzene) derivative with a triplet ground state, we have investigated tetrasubstitution by −F, −NH2, −CH3, and −NO2 groups. These were predicted to reduce the singlet−triplet gap, but none led to a triplet ground state because of unexpected destabilization of one of the radical orbitals. This effect is likely the result of rehybridization of the substituted C atom, which has been observed for substituted benzene and perturbs the side σ and σ* orbital energies of the phenyl ring. The role of substituent rotation on the energy difference between the two nominally singly occupied orbitals (S and A) was then investigated. The energy of the A radical orbital was found to be much more sensitive to perturbations within the σ C−C framework than the S MO. Consequently, we believe that rehybridization of the ring carbons destabilizes the A radical orbital and can lead to large singlet−triplet splittings. To test this hypothesis, calculations on a p-benzyne with 2,6 sub...