Diboron- and Diaza-Doped Anthracenes and Phenanthrenes: Their Electronic Structures for Being Singlet Fission...

We used quantum chemistry methods at the levels of mixed-reference spin-flip time-dependent density functional theory and multireference perturbation theory to study diboron- and diaza-doped anthracenes and phenanthrenes. This class of structures recently surged as potential singlet fission chromophores. We studied electronic structures of their excited states and clarified the reasons why they satisfy or fail to satisfy the energy criteria for singlet fission chromophores. Many studied structures have their S₁ states not dominated by HOMO → LUMO excitation, so they cannot be described using the conventional two site model. This is attributed to frontier orbital energy shifts induced by the doping and different charge-transfer energies in different one-electron singlet excitations or, in other words, different polarizations of hole and/or particle orbitals in their S₁ and T₁ states. There is a mirror relation between the orbital energy shifts induced by diboron- and diaza-dopings, which together with alternant hydrocarbon pairings of occupied and unoccupied orbitals, leads to more mirror relations between the excited states of the two types of doped structures.