Optimal arrangements of 1,3-diphenylisobenzofuran molecule pairs for fast singlet fission

Abstract

A simplified version of the frontier orbital model has been applied to pairs of C₂, C_2v, C_s, and C₁ symmetry 1,3-diphenylisobenzofuran rotamers to determine their best packing for fast singlet fission (SF). For each rotamer the square of the electronic matrix element for SF was calculated at 2.2 × 10⁹ pair geometries and a few thousand most significant physically accessible local maxima were identified in the six-dimensional space of mutual arrangements. At these pair geometries, SF energy balance was evaluated, relative SF rate constants were approximated using Marcus theory, and the SF rate constant k_SF was maximized by further optimization of the geometry of the molecular pair. The process resulted in 142, 67, 214, and 291 unique geometries for the C₂, C_2v, C_s, and C₁ symmetry molecular pairs, respectively, predicted to be superior to the C₂ symmetrized known crystal pair structure. These optimized pair geometries and their triplet biexciton binding energies are reported as targets for crystal engineering and/or covalent dimer synthesis, and as possible starting points for high-level pair geometry optimizations.