Inorganic Chemistry
Forum Article
J. Artificial Photosynthesis: Where Are We Now? Where Can We Go?
J. Photochem. Photobiol., C 2015, 25, 32−45.
(12) Baldo, M. A.; Lamansky, S.; Burrows, P. E.; Thompson, M. E.;
Forrest, S. R. Very High-Efficiency Green Organic Light-Emitting
Devices Based on Electrophosphorescence. Appl. Phys. Lett. 1999, 75,
4−6.
(13) Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.;
Lee, H.-E.; Adachi, C.; Burrows, P. E.; Forrest, S. R.; Thompson, M.
E. Highly Phosphorescent Bis-Cyclometalated Iridium Complexes:
Synthesis, Photophysical Characterization, and Use in Organic Light
Emitting Diodes. J. Am. Chem. Soc. 2001, 123, 4304−4312.
(14) Borek, C.; Hanson, K.; Djurovich, P. I.; Thompson, M. E.;
Aznavour, K.; Bau, R.; Sun, Y.; Forrest, S. R.; Brooks, J.; Michalski, L.;
Brown, J. Highly Efficient, Near-Infrared Electrophosphorescence
from a Pt-Metalloporphyrin Complex. Angew. Chem., Int. Ed. 2007,
46, 1109−1112.
longer-wavelength region was observed for [Ru-
(dmb)2(8pyq)]2+ compared with the reference complexes
without any six-membered chelate rings. Although intense
absorption in the broad UV−visible is advantageous for the
applications as photosensitizers, the emission from [Ru-
(dmb)2(8pyq)]2+ was quite weak, presumably due to the
structural distortion of the 8pyq ligand in the complex. On the
basis of the results obtained in the present study, new and
novel light absorbers/triplet emitters will be developed in the
near future.
ASSOCIATED CONTENT
* Supporting Information
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S
The Supporting Information is available free of charge on the
(15) Yersin, H.; Rausch, A. F.; Czerwieniec, R.; Hofbeck, T.; Fischer,
T. The Triplet State of Organo-Transition Metal Compounds. Triplet
Harvesting and Singlet Harvesting for Efficient OLEDs. Coord. Chem.
Rev. 2011, 255, 2622−2652.
Synthesis and detailed results of theoretical calculations
(16) Chi, Y.; Tong, B.; Chou, P.-T. Metal Complexes with Pyridyl
Azolates: Design, Preparation and Applications. Coord. Chem. Rev.
2014, 281, 1−25.
AUTHOR INFORMATION
Corresponding Author
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(17) Haga, M.-a.; Matsumura-Inoue, T.; Shimizu, K.; Sato, G. P.
Notes Ligand Additivity in the Oxidation Potentials of Bidentate
Mixed-Ligand Ruthenium(II) Complexes. J. Chem. Soc., Dalton Trans.
1989, 371−373.
ORCID
(18) Allard, M. M.; Odongo, O. S.; Lee, M. M.; Chen, Y.-J.;
Endicott, J. F.; Schlegel, H. B. Effects of Electronic Mixing in
Ruthenium(II) Complexes with Two Equivalent Acceptor Ligands.
Spectroscopic, Electrochemical, and Computational Studies. Inorg.
Chem. 2010, 49, 6840−6852.
(19) Ito, A.; Stewart, D. J.; Fang, Z.; Brennaman, M. K.; Meyer, T. J.
Sensitization of Ultra-Long-Range Excited-State Electron Transfer by
Energy Transfer in a Polymerized Film. Proc. Natl. Acad. Sci. U. S. A.
2012, 109, 15132−15135.
(20) Ito, A.; Stewart, D. J.; Knight, T. E.; Fang, Z.; Brennaman, M.
K.; Meyer, T. J. Excited-State Dynamics in Rigid Media: Evidence for
Long-Range Energy Transfer. J. Phys. Chem. B 2013, 117, 3428−3438.
(21) Ito, A.; Fang, Z.; Brennaman, M. K.; Meyer, T. J. Long-Range
Photoinduced Electron Transfer Dynamics in Rigid Media. Phys.
Chem. Chem. Phys. 2014, 16, 4880−4891.
Notes
The authors declare no competing financial interest.
REFERENCES
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(1) Thompson, D. W.; Ito, A.; Meyer, T. J. [Ru(bpy)3]2+* and Other
Remarkable Metal-to-Ligand Charge Transfer (MLCT) Excited
States. Pure Appl. Chem. 2013, 85, 1257−1305.
̈
(2) O’Regan, B.; Gratzel, M. A Low-Cost, High-Efficiency Solar Cell
Based on Dye-Sensitized Colloidal TiO2 Films. Nature 1991, 353,
737−740.
(3) O’Regan, B.; Schwartz, D. T. Large Enhancement in Photo-
current Efficiency Caused by UV Illumination of the Dye-Sensitized
Heterojunction TiO2/RuLL’NCS/CuSCN: Initiation and Potential
Mechanisms. Chem. Mater. 1998, 10, 1501−1509.
(22) Suzuki, K.; Kobayashi, A.; Kaneko, S.; Takehira, K.; Yoshihara,
T.; Ishida, H.; Shiina, Y.; Oishi, S.; Tobita, S. Reevaluation of
Absolute Luminescence Quantum Yields of Standard Solutions Using
a Spectrometer with an Integrating Sphere and a Back-Thinned CCD
Detector. Phys. Chem. Chem. Phys. 2009, 11, 9850−9860.
(23) Ishida, H.; Tobita, S.; Hasegawa, Y.; Katoh, R.; Nozaki, K.
Recent Advances in Instrumentation for Absolute Emission Quantum
Yield Measurements. Coord. Chem. Rev. 2010, 254, 2449−2458.
(24) Parker, C. A.; Rees, W. T. Correction of Fluorescence Spectra
and Measurement of Fluorescence Quantum Efficiency. Analyst 1960,
85, 587−600.
̈
(4) Gratzel, M. Dye-Sensitized Solar Cells. J. Photochem. Photobiol.,
C 2003, 4, 145−153.
(5) Kinoshita, T.; Nonomura, K.; Joong Jeon, N.; Giordano, F.;
Abate, A.; Uchida, S.; Kubo, T.; Seok, S. I.; Nazeeruddin, M. K.;
̈
Hagfeldt, A.; Gratzel, M.; Segawa, H. Spectral splitting photovoltaics
using perovskite and wideband dye-sensitized solar cells. Nat.
Commun. 2015, 6, 8834.
(6) Kalyanasundaram, K. Photophysics, Photochemistry and Solar
Energy Conversion with Tris(bipyridyl)ruthenium(II) and Its
Analogues. Coord. Chem. Rev. 1982, 46, 159−244.
(25) Valeur, B. Molecular Fluorescence: Principles and Applications;
Wiley-VCH: Weinheim: New York, 2006.
(7) Meyer, T. J. Chemical Approaches to Artificial Photosynthesis.
Acc. Chem. Res. 1989, 22, 163−170.
(26) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson,
G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.;
Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J.
V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.;
Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson,
T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.;
Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Throssell, K.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.;
Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov,
V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.;
Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.;
(8) Alstrum-Acevedo, J. H.; Brennaman, M. K.; Meyer, T. J.
Chemical Approaches to Artificial Photosynthesis. 2. Inorg. Chem.
2005, 44, 6802−6827.
(9) Sato, S.; Arai, T.; Morikawa, T.; Uemura, K.; Suzuki, T. M.;
Tanaka, H.; Kajino, T. Selective CO2 Conversion to Formate
Conjugated with H2O Oxidation Utilizing Semiconductor/Complex
Hybrid Photocatalysts. J. Am. Chem. Soc. 2011, 133, 15240−15243.
(10) Sato, S.; Matubara, Y.; Koike, K.; Falkenstrom, M.; Katayama,
T.; Ishibashi, Y.; Miyasaka, H.; Taniguchi, S.; Chosrowjan, H.;
Mataga, N.; Fukazawa, N.; Koshihara, S.; Onda, K.; Ishitani, O.
Photochemistry of fac-[Re(bpy)(CO)3Cl]. Chem. - Eur. J. 2012, 18,
15722−15734.
(11) House, R. L.; Iha, N. Y. M.; Coppo, R. L.; Alibabaei, L.;
Sherman, B. D.; Kang, P.; Brennaman, M. K.; Hoertz, P. G.; Meyer, T.
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