Thiophene-Based Double Helices: Radical Cations with SOMO-HOMO Energy Level Inversion.

ABSTRACT: We report relatively persistent, open-shell thiophene-based double helices, radical cations 1^•+ -TMS₁₂ and 2^•+ -TMS₈ . Closed-shell neutral double helices, 1-TMS₁₂ and 2-TMS₈ , have nearly identical first oxidation potentials, E ^+/0  ≈ +1.33 V, corresponding to reversible oxidation to their radical cations. The radical cations are generated, using tungsten hexachloride in dichloromethane (DCM) as an oxidant, E ^+/0  ≈ +1.56 V. EPR spectra consist of a relatively sharp singlet peak with an unusually low g-value of 2.001-2.002, thus suggesting exclusive delocalization of spin density over π-conjugated system consisting of carbon atoms only. DFT computations confirm these findings, as only negligible fracti

SUBMITTER: Rajca A 

PROVIDER: S-EPMC8688166 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature