Excited-state photophysical processes in a molecular system containing perylene bisimide and zinc porphyrin chromophores.

Multichromophoric systems with efficient photoinduced excited-state processes are important for the conversion of solar energy in artificial photosynthesis. However, a low molecular absorption coefficient of these multichromophoric systems in the near-infrared region limits their power conversion efficiency in organic solar cells. It is critical to design molecules with a broad absorption range in the whole spectral region, to better harvest solar energy, and to reveal their important multiple-step photophysical processes for the design of organic solar cells. Here, we investigate a novel compound having three chromophores, namely two near-by N,N'-bis(1-pentyl)hexyl-3,4,9,10-perylenebiscarboximide (PDI) units linked to a zinc porphyrin core side by side (in the form of PDI-ZnPor-PDI), which absorbs solar energy ranging from the ultraviolet (UV) to near-infrared regions. The photophysical behavior of PDI-ZnPor-PDI in both film and solution forms, has been investigated using steady-state and transient spectroscopy measurements. Charge-transfer species and triplet excited-state species are observed, the excited-state evolutions of which are monitored using molecular vibrations as probes. These observations support the idea that PDI-ZnPor-PDI on photoexcitation generates the radical anion and triplet species of the PDI unit (PDI˙- and 3PDI*). Our results demonstrate the effect of solid film state on the photophysical properties in such multichromophoric system, and are valuable for guiding the design and utilization of novel near-infrared electron donors or acceptors for use in organic solar cells.