Inorganic Chemistry
Article
Topics in Organometallic Chemistry; Lees, A. J., Ed.; Springer: New
York, 2010; Vol. 29, pp 1−35.
CONCLUSIONS
■
This work showed, for the first time, photoinduced trans-to-cis
isomerization of a stilbene-like ligand coordinated to a Re(I)
polypyridyl complex on TiO2. On the surface, trans-to-cis
photoisomerization and electron injection are competitive
pathways for excited state deactivation and can be controlled
by the selection of ligands and/or by using semiconductors
with different conduction band energies. For fac-[Re-
(CO)3(phen)(trans-stpyCOOH)]+ on TiO2, the photoisome-
rization process occurs with an apparent quantum yield of the
(8) Itokazu, M. K.; Polo, A. S.; Murakami Iha, N. Y. J. Photochem.
Photobiol., A 2003, 160, 27−32.
(9) Wagenknecht, P. S.; Ford, P. C. Coord. Chem. Rev. 2011, 255,
591−616.
(10) Hugel, T.; Holland, N. B.; Cattani, A.; Moroder, L.; Seitz, M.;
Gaub, H. E. Science 2002, 296, 1103−1106.
(11) Balzani, V.; Credi, A.; Venturi, M. ChemPhysChem 2008, 9,
202−220.
(12) Santoni, M. P.; Hanan, G. S.; Hasenknopf, B.; Proust, A.;
Nastasi, F.; Serroni, S.; Campagna, S. Chem. Commun. 2011, 47,
3586−3588.
same order as in solution (Φ = 0.23
0.03; 404 nm
irradiation) and can be considered the majority process. The
photoproduct, fac-[Re(CO)3(phen)(cis-stpyCOOH)]+, is emis-
sive in solution, but when adsorbed on TiO2, its luminescence
is completely quenched by electron injection. This explains the
rise in photocurrent as the concentration of the cis-isomer
increases. The different behaviors of both isomers are
rationalized in terms of the nature of the low lying excited
(13) Polo, A. S.; Itokazu, M. K.; Frin, K. M.; Patrocinio, A. O. T.;
Murakami Iha, N. Y. Coord. Chem. Rev. 2006, 250, 1669−1680.
(14) Vlcek, A., Jr. Ultrafast excited-state processes in Re(I) carbonyl-
diimine complexes: From excitation to photochemistry. In Topics in
Organometallic Chemistry; Lees, A. J., Ed.; Springer: New York, 2010;
Vol. 29, pp 73−114.
(15) Lin, J. L.; Chen, C. W.; Sun, S. S.; Lees, A. J. Chem. Commun.
2011, 47, 6030−6032.
(16) Tapolsky, G.; Duesing, R.; Meyer, T. J. Inorg. Chem. 1990, 29,
2285−2297.
3
3
state, ILtrans‑stpyCOOH in the trans-isomer and MLCTRe→phen in
the cis-one. Thus, the electrical signal is controlled by a
molecular motion, which opens the possibility of using the
system in molecular devices.
(17) Gholamkhass, B.; Mametsuka, H.; Koike, K.; Tanabe, T.; Furue,
M.; Ishitani, O. Inorg. Chem. 2005, 44, 2326−2336.
(18) Christ, C. S.; Yu, J.; Zhao, X. H.; Palmore, G. T. R.; Wrighton,
M. S. Inorg. Chem. 1992, 31, 4439−4440.
ASSOCIATED CONTENT
■
(19) Patrocinio, A. O. T.; Murakami Iha, N. Y. Inorg. Chem. 2008, 47,
10851−10857.
S
* Supporting Information
1H NMR spectral data in CD3CN for ligands and complexes,
trans-to-cis photoisomerization quantum yields for fac-[Re-
(CO)3(phen)(trans-stpyCOOH)]+ on TiO2 (λirr = 404 nm) at
different surface loadings as a function of irradiation time, and
time-resolved emission spectra at different delay times of fac-
[Re(CO)3(phen)(cis-stpyCOOH)]+ in acetonitrile. This ma-
terial is available free of charge via the Internet at http://pubs.
(20) Frin, K. M.; Murakami Iha, N. Y. J. Braz. Chem. Soc. 2006, 17,
1664−1671.
(21) Gindensperger, E.; Koppel, H.; Daniel, C. Chem. Commun.
2010, 46, 8225−8227.
(22) Bossert, J.; Daniel, C. Chem.Eur. J. 2006, 12, 4835−4843.
(23) Kayanuma, M.; Daniel, C.; Koppel, H.; Gindensperger, E. Coord.
̈
Chem. Rev. 2011, 255, 2693−2703.
(24) Wenger, O. S.; Henling, L. M.; Day, M. W.; Winkler, J. R.; Gray,
H. B. Inorg. Chem. 2004, 43, 2043−2048.
(25) Yam, V. W. W.; Lan, V. C. Y.; Wu, L. X. J .Chem. Soc., Dalton
Trans. 1998, 1461−1468.
AUTHOR INFORMATION
■
Corresponding Author
Notes
(26) Polo, A. S.; Itokazu, M. K.; Murakami Iha, N. Y. J. Photochem.
Photobiol., A 2006, 181, 73−78.
(27) Busby, M.; Matousek, P.; Towrie, M.; Vlcek, A., Jr. J. Phys.
Chem. A 2005, 109, 3000−3008.
The authors declare no competing financial interest.
(28) Patrocinio, A. O. T.; Brennaman, M. K.; Meyer, T. J.; Murakami
Iha, N. Y. J. Phys. Chem. A 2010, 114, 12129−12137.
(29) Hatchard, C. G.; Parker, C. A. Proc. R. Soc. London, A 1956, 235,
518−536.
ACKNOWLEDGMENTS
■
This work was supported by Fundaca
̧
o de Amparo a
̀
Pesquisa
̧ o de Amparo a Pesquisa de
̃
̃
(30) Chiang, M. C.; Hartung, W. H. J. Org. Chem. 1945, 10, 21−25.
(31) Itokazu, M. K.; Polo, A. S.; de Faria, D. L. A.; Bignozzi, C. A.;
Murakami Iha, N. Y. Inorg. Chim. Acta 2001, 313, 149−155.
(32) Patrocinio, A. O. T.; Paterno, L. G.; Murakami Iha, N. Y. J.
Photochem. Photobiol., A 2009, 205, 23−27.
(33) Patrocínio, A. O. T.; Paniago, E. B.; Paniago, R. M.; Murakami
Iha, N. Y. Appl. Surf. Sci. 2008, 254, 1874−1879.
(34) Frin, K. P. M.; Itokazu, M. K.; Murakami Iha, N. Y. Inorg. Chim.
Acta 2010, 363, 294−300.
(35) Frin, K. P. M.; Zanoni, K. P. S.; Murakami Iha, N. Y. Inorg.
Chem. Commun. 2012, 20, 105−107.
(36) Brennaman, M. K.; Patrocinio, A. O. T.; Song, W.; Jurss, J. W.;
Concepcion, J. J.; Hoertz, P. G.; Traub, M. C.; Murakami Iha, N. Y.;
Meyer, T. J. ChemSusChem 2011, 4, 216−227.
(37) Gallagher, L. A.; Serron, S. A.; Wen, X. G.; Hornstein, B. J.;
Dattelbaum, D. M.; Schoonover, J. R.; Meyer, T. J. Inorg. Chem. 2005,
44, 2089−2097.
de Sao Paulo, FAPESP, Fundaca
̃
Minas Gerais, FAPEMIG, and Conselho Nacional de
́
́
Desenvolvimento Cientifico e Tecnologico, CNPq. We would
like to acknowledge Prof. Thomas J. Meyer for discussion and
the manuscript reviewing of the first version.
REFERENCES
■
(1) Saha, S.; Stoddart, J. F. Chem. Soc. Rev. 2007, 36, 77−92.
(2) Balzani, V.; Bergamini, G.; Ceroni, P. Coord. Chem. Rev. 2008,
252, 2456−2469.
(3) Morris, A. J.; Meyer, G. J.; Fujita, E. Acc. Chem. Res. 2009, 42,
1983−1994.
(4) Pellegrin, Y.; Odobel, F. Coord. Chem. Rev. 2011, 255, 2578−
2593.
(5) Gratzel, M. Acc. Chem. Res. 2009, 42, 1788−1798.
̈
(6) Song, W. J.; Chen, Z. F.; Brennaman, M. K.; Concepcion, J. J.;
Patrocinio, A. O. T.; Murakami Iha, N. Y.; Meyer, T. J. Pure Appl.
Chem. 2011, 83, 749−768.
(38) Worl, L. A.; Duesing, R.; Chen, P. Y.; Dellaciana, L.; Meyer, T. J.
J. Chem. Soc., Dalton Trans. 1991, 849−858.
(39) Polo, A. S.; Murakami Iha, N. Y. Sol. Energy Mater. Sol. Cells
2006, 90, 1936−1944.
(7) Kumar, A.; Sun, S. S.; Lees, A. J. Photophysics and
photochemistry of organometallic rhenium diimine complexes. In
G
dx.doi.org/10.1021/ic3028572 | Inorg. Chem. XXXX, XXX, XXX−XXX