Functionalization of Clar's Goblet Diradical with Heteroatoms: Tuning the Excited-State Energies to Promote...

The ground-state spin multiplicity as well as the energy difference between the lowest-energy spin-singlet (S₁) and spin-triplet (T₁) excited states of topologically frustrated organic (diradical) molecules can be tuned by doping with a pair of heteroatoms (N or B atoms). We have thus systematically studied here a set of Clar's Goblet derivatives upon a controlled substitution at different C sites, to alter the electronic structure of the molecules and disclose the positions at which: (i) the ground-state multiplicity becomes a closed-shell singlet and (ii) the energy difference between S₁ and T₁ is considerably small (i.e., below 0.1-0.2 eV to induce a triplet exciton recovery upon thermal effects). This electronic structure outcome is driven by strong correlation effects; therefore, we have here applied a variety of single-reference [TD-DFT, CIS(D), SCS-CC2] and multireference [CASSCF, NEVPT2, RAS-srDFT] methods. For TD-DFT, we have covered global hybrid (PBE0, M06-2X), range-separated hybrid (ωB97X), and double-hybrid (PBE-QIDH, SOS1-PBE-QIDH, and PBE0-2) functionals to ascertain whether the results were highly dependent on the functional choice. Overall, we found that the heterosubstitution strategy could largely modify the electronic and optical properties of the pristine diradical system, with these organic forms thus constituting a new set of compounds with further optoelectronic applications.