The Lack of Triplet Fusion for an Intramolecular Singlet Fission Chromophore: The Expected, the Unexpected, and a Reconciliation

Singlet fission (SF) has the potential to play a key role in photovoltaics since it generates a larger number of longer-lived triplet excitons after photoabsorption. Intramolecular SF (iSF) is of special interest since it enables tuning of SF efficiency by adjusting interchromophore configuration through covalent interaction. However, as elaborated in the present work, iSF chromophores are doomed to dissatisfy one general thermodynamic criterion for all SF chromophores, intramolecular or not: E ( T 2 ) ≥ 2 E ( T 1 ), and therefore, the fusion of two triplet excitons to one triplet exciton is thermodynamically favorable. In our nonadiabatic quantum dynamics simulation for a model iSF chromophore, this expected fusion does not occur, because of the inefficient intersystem crossing hidden under the cover of internal conversion of the triplet fusion. A reconciliation is achieved between the dissatisfaction of E ( T 2 ) ≥ 2 E ( T 1 ) and the large tetraradical character for general iSF chromophores.