Triplet–singlet gap in structurally flexible organic diradicals

A key factor in the search of high-spin ground state purely organic molecules concerns the effect of the inherent non-rigid structures on the magnetic and optical properties. This structural feature has not been properly addressed in previous theoretical works. Here, based on the experimentally characterized high-spin ground state of dendritic and star-branched polyradicals, we study four alternant hydrocarbon biradicals that intend to model these effects and, at the same time, provide a first step toward understanding more extended experimental structures. A series of density functional theory (DFT) and of wave function-based methods have been used to explore the richness of structural minima in the corresponding potential energy surfaces and to discuss its effect on the triplet–singlet gap of the proposed model systems. For a given model, the DFT-based B3LYP, M06-2X and MN-12SX methods provide a consistent description. Likewise, a multiconfigurational quasi-degenerate perturbation theory approach with the minimal π space as CASSCF reference is found to provide unbiased results. Despite the conformational richness found for these systems, they all can be described by a reduced set of values referred to only two structural parameters, being those the dihedral angles between the phenyl rings. For a given model, there is no significant change in the triplet–singlet gap depending on the chosen local minima.