Journal of Physical Chemistry C vol:111 issue:12 pages:4861-4870
Shape persistent perylene diimide (PDI) multichromophores incorporating ethynylene bridges have been synthesized in high yield via palladium-catalyzed Hagihara coupling, which provides compounds with no rotational or constitutional isomerism in contrast to polyphenylene dendrimers. Their excited-state pathways have been studied at the ensemble and at the single-molecule level and compared to several model compounds. In an apolar solvent, energy hopping and/or energy transfer between the chromophoric units are the dominating processes. In a polar medium, energy hopping is still operative, but electron transfer from the phenyl ethynylene bridge to the chromophore occurs if the former is connected to the bay area of PDI. This effect should be considered when further developing this type of multichromophore, as this nonradiative deactivation process might be unwanted for applications such as optical and electronic devices. At the single-molecule level, the fluorescence intensity traces are characterized by rich on-off dynamics, which we attribute to oxygen-enhanced intersystem crossing leading to the formation of a long-lived dark charge-separated state.