Room Temperature Phosphorescence in Crystalline Iodinated Eumelanin Monomer.

We report the room temperature phosphorescence upon iodination on a crystalline eumelanin monomer with shielded hydroxyl moieties, ethyl 5,6-dimethoxyindole-2-carboxylate (DMICE). Ultrafast intersystem crossing (ISC) is observed in the iodinated (IDMICE) as well as brominated (BDMICE) analogues of the eumelanin monomer derivative in solution. The triplet quantum yields (φ) and intersystem crossing rates (k) of the halogenated eumelanin derivatives are =25.

Modulating singlet fission through interchromophoric rotation.

Singlet fission (SF) is a spin-allowed, exciton-multiplying phenomenon that can be utilized to improve the efficiency of organic solar cells. It is well-understood that SF is sensitive to the local crystal morphology and an appropriately balanced coupling is essential to facilitate efficient SF. In this study, we show how the interchromophoric rotation selectively modulates the interaction between the monomer frontier molecular orbitals, promoting both fast and exothermal SF.