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

A simplified version of the frontier orbital model has been applied to pairs of C2, C2v, Cs, 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 kSF 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, C2v, Cs, 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.