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International Journal of Photoenergy
Volume 2011 (2011), Article ID 204639, 8 pages
Research Article

Synthesis and Application of New Ruthenium Complexes Containing β-Diketonato Ligands as Sensitizers for Nanocrystalline TiO2 Solar Cells

1International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
2Advanced Photovoltaics Center, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
3Center of Excellence for Research in Engineering Materials (CEREM), College of Engineering, King Saud University, Riyadh 11421, Saudi Arabia

Received 30 March 2011; Accepted 4 May 2011

Academic Editor: Mohamed Sabry Abdel-Mottaleb

Copyright © 2011 Ashraful Islam et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Five heteroleptic ruthenium complexes having different β-diketonato ligands, [Ru(tctpy)(dppd)(NCS)] (1), [Ru(tctpy)(pd)(NCS)] (2), [Ru(tctpy)(tdd)(NCS)] (3), [Ru(tctpy)(mepd)(NCS)] (4), and [Ru(tctpy)(tmhd)(NCS)] (5), where tctpy = 4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine, pd = pentane-2,4-dione, mepd = 3-methylpentane-2,4-dione, tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, tdd = tridecane-6,8-dione, and dppd = 1,3-diphenylpropane-1,3-dione, were synthesized and characterized. These heteroleptic complexes exhibit a broad metal-to-ligand charge transfer absorption band over the whole visible range extending up to 950 nm. The low-energy absorption bands and the E (Ru3+/2+) oxidation potentials in these complexes could be tuned to about 15 nm and 110 mV, respectively, by choosing appropriate β-diketonate ligands. Molecular orbital calculation of complex 1 shows that the HOMO is localized on the NCS ligand and the LUMO is localized on the tctpy ligand, which is anchored to the TiO2 nanoparticles. The β-diketonato-ruthenium(II)-polypyridyl sensitizers, when anchored to nanocrystalline TiO2 films for light to electrical energy conversion in regenerative photoelectrochemical cells, achieve efficient sensitization to TiO2 electrodes with increasing activity in the order 5 < 4 < 3 2 < 1. Under standard AM 1.5 sunlight, the complex 1 yielded a short-circuit photocurrent density of 16.7 mA/cm2, an open-circuit voltage of 0.58 V, and a fill factor of 0.64, corresponding to an overall conversion efficiency of 6.2%. A systematic tuning of HOMO energy level shows that an efficient sensitizer should possess a ground-state redox potential value of >+.53 V versus SCE.