Efficient Dye-Sensitized Solar Cells Based on a New Class of Doubly Concerted Companion Dyes

To develop efficient dye-sensitized solar cells (DSSCs), concerted companion (CC) dyes XW60-XW63 constructed from the covalent linkage of a strapped porphyrin dye unit and an organic dye unit have been reported to exhibit panchromatic absorption and excellent photovoltaic performance. However, these CC dyes only afforded moderate V-OC values of ca. 763 mV, demonstrating relatively weak antiaggregation ability, which remains an obstacle for further enhancing the photovoltaic behavior. To address this problem, we herein develop porphyrin dyes XW77-XW80 with the macrocycles wrapped with alkoxy chains of various lengths (OC6H13-OC22H45) and the corresponding CC dyes XW81-XW84 containing these porphyrin dye units. Interestingly, the new CC dyes XW81-XW83 exhibit increasing V-OC from 745 to 784 mV with the chain lengths extended from C6 to C18, and a lowered V-OC of 762 mV was obtained for XW84 when the chain length was further extended to C22. As a result, XW83 afforded the highest PCE of 12.2%, which is, to the best of our knowledge, the record efficiency for the iodine electrolyte-based solar cells sensitized with a single dye. These results can be rationalized by the so-called doubly concerted companion (DCC) effects, that is, the two subdye units exhibit not only complementary absorption but also concerted antiaggregation with the long wrapping chains on the porphyrins unit simultaneously protecting the porphyrin macrocycle and the neighboring organic subdye unit, thus affording panchromatic absorption and strong antiaggregation and anticharge-recombination ability. These results provide a new approach for constructing a class of DCC dyes to achieve high-performance DSSCs without using any antiaggregating coadsorbent or absorption-enhancing cosensitizer.