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.