| Summary: | Natural-chlorophyll-related porphyrins, including (2H, Zn, Cu)-protoporphyrin IX (Por-1) and Zn-mesoporphyrin IX (Por-2), and chlorins, including chlorin e6 (Chl-1), chlorin e4 (Chl-2), and rhodin G7 (Chl-3), have been used in dye-sensitized solar cells (DSSCs). For porphyrin sensitizers that have vinyl groups at the β-positions, zinc coordinated Por-1 gives the highest solar-energy-to-electricity conversion efficiency (h) of up to 2.9%. Replacing the vinyl groups of ZnPor-1 with ethyl groups increases the open-circuit voltage (Voc) from 0.61 V to 0.66 V, but decreases the short-circuit current (Jsc) from 7.0 mA·cm−2 to 6.1 mA·cm−2 and the value of h to 2.8%. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations suggest that the higher Jsc values of Zn-based porphyrin sensitizers result from the favorable electron injection from the LUMO at higher energy levels. In the case of the chlorin sensitizers, the number of carboxyl protons has a large effect on the photovoltaic performance. Chl-2 with two carboxyl protons gives much higher values of Jsc, Voc, and h than does Chl-1 with three carboxyl protons. Replacing the protons of Chl-1 with sodium ions can substantially improve the photovoltaic performance of Chl-1-based solar cells. Furthermore, the sodium salt of Chl-3 with an aldehyde group at the C7 position shows poorer photovoltaic performance than does the sodium salt of Chl-1 with methyl groups at the C7 position. This is due to the low light-harvesting capability of Chl-3.
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