High-Spin Diradical Dication of Chiral π-Conjugated Double Helical Molecule.

ABSTRACT: We report an air-stable diradical dication of chiral D₂-symmetric conjoined bis[5]diazahelicene with an unprecedented high-spin (triplet) ground state, singlet triplet energy gap, ΔE_ST = 0.3 kcal mol^-1. The diradical dication possesses closed-shell (Kekulé) resonance forms with 16 π-electron perimeters. The diradical dication is monomeric in dibutyl phthalate (DBP) matrix at low temperatures, and it has a half-life of more than 2 weeks at ambient conditions in the presence of excess oxidant. A barrier of ∼35 kcal mol^-1 has been experimentally determined for inversion of configuration in the neutral conjoined bis[5]diazahelicene, while the inversion barriers in its radical cation and diradical dication were predicted by the DFT compu

SUBMITTER: Shu C 

PROVIDER: S-EPMC7039282 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature