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̈
Figure 4. Temporal stabilities of 1−4/TiO2 submerged in water at pH
7.0. Data for N3 are also shown to highlight the enhanced stability
engendered by the cooperatively binding anchoring groups of 4.
was therefore rewarding to find that 4/TiO2 revealed no
evidence of dye desorption over the same period of time.
Indeed, the fraction of 4 on the surface was found to remain
essentially static over 20 days under said conditions. This result
indicates that the cooperative action of the three anchoring
groups has a positive effect in stabilizing the dye on the surface.
In contrast, substrates stained with N3 led to a loss of ca. 50%
surface coverage within 2 h.
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This study has demonstrated a simple molecular design
strategy for exploiting the favorable properties of distinctive
anchoring groups. The placement of carboxylates on the ligand
responsible for electron communication with the surface and
strongly binding phosphonates between the surface and the
opposing ligand achieves both charge transfer and a robust dye/
TiO2 motif. This widely applicable strategy has far-reaching
implications for the sensitization of semiconducting materials,
particularly in aqueous media. Future studies will be focused on
demonstrating this strategy in the context of (photo)-
electrocatalytic schemes and developing more strongly
absorbing dyes in order to achieve higher PCEs in the DSSC.
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(22) DFT calculations were performed using the B3LYP hybrid
functional with the pseudopotential LANL2DZ basis set for Ru and
the 6-31G* basis set for all other atoms.
(23) Robson, K. C. D.; Bomben, P. G.; Berlinguette, C. P. Dalton
Trans. 2012, 41, 7814.
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ASSOCIATED CONTENT
* Supporting Information
Full experimental, synthetic, and structural details. This material
■
S
Baker, R.; Gratzel, M. J. Phys. Chem. B 2005, 109, 21818.
̈
(26) Suto, K.; Konno, A.; Kawata, Y.; Tasaka, S.; Sugita, A. Chem.
Phys. Lett. 2012, 536, 45.
AUTHOR INFORMATION
Corresponding Author
Notes
(27) Bazzan, G.; Deneault, J. R.; Kang, T.-S.; Taylor, B. E.; Durstock,
M. F. Adv. Funct. Mater. 2011, 21, 3268.
(28) Ganbold, E.-O.; Lee, Y.; Lee, K.; Kwon, O.; Joo, S.-W. Chem.
Asian J. 2010, 5, 852.
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
C.P.B. is grateful for support from the Natural Science and
Engineering Research Council, Canada Research Chairs,
Canadian Foundation for Innovation, Canada School of Energy
and Environment, and the Alfred P. Sloan Foundation.
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dx.doi.org/10.1021/ja310965h | J. Am. Chem. Soc. 2013, 135, 1692−1695