Ruthenium sensitizers with 2,2′-bipyrimidine or a 5,5′-disubstituted 2,2′-bipyrimidine ligand

Synthesis, photo- and electrochemical properties, and application to dye-sensitized solar cells

Hironobu Ozawa, Hiroki Kawaguchi, Yu Okuyama, Hironori Arakawa

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Novel ruthenium sensitizers with 2,2′-bipyrimidine (TUS-26) or a 2,2′-bipyrimidine derivative bearing two 5-hexyl-2,2′-bithiophene units at the 5,5′-positions (TUS-27) have been synthesized for application in dye-sensitized solar cells. TUS-27 shows a strong absorption at around 460 nm, mainly attributed to a π-π* transition in the 5,5′-disubstituted 2,2′-bipyrimidine ligand, and an onset wavelength of the absorption spectrum that is redshifted by about 50 nm relative to those of structurally analogous sensitizers (cis-[Ru(dcbpy)(bpy)(NCS)2] and N719). The energy level of the LUMO of TUS-27 is relatively close to that of the conduction band of TiO2. Dye-sensitized solar cells containing TUS-26 and TUS-27 showed much poorer performances than those containing cis-[Ru(dcbpy)(bpy)(NCS)2] and N719, even though an electrolyte containing no 4-tert-butylpyridine was used to adjust the energy of the conduction band of TiO2. The results of DFT calculations indicated that both unfavorable populations of LUMO and LUMO+1, and the lower energy level of LUMO+1, contribute to the much poorer solar cell performances of the TUS sensitizers. In addition, photovoltaic measurements also suggested that enhancement of backward electron transfer from the conduction band of TiO 2 to the one-electron-oxidized form of the dye or to I 3 - in the electrolyte is another reason for the inferior performances of the TUS sensitizers. Two novel ruthenium sensitizers with a 2,2′-bipyrimidine (TUS-26) or a 2,2′-bipyrimidine derivative bearing two 5-hexyl-2,2′-bithiophene units at the 5,5′-positions (TUS-27) have been synthesized. The performances of these sensitizers in dye-sensitized solar cells have been investigated.

Original languageEnglish
Pages (from-to)5187-5195
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number29
DOIs
Publication statusPublished - Oct 1 2013
Externally publishedYes

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Ruthenium
Bearings (structural)
Conduction bands
Electrochemical properties
Ligands
Electron energy levels
Electrolytes
Derivatives
Electrons
Discrete Fourier transforms
Absorption spectra
Solar cells
Coloring Agents
Wavelength
Dye-sensitized solar cells

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

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title = "Ruthenium sensitizers with 2,2′-bipyrimidine or a 5,5′-disubstituted 2,2′-bipyrimidine ligand: Synthesis, photo- and electrochemical properties, and application to dye-sensitized solar cells",
abstract = "Novel ruthenium sensitizers with 2,2′-bipyrimidine (TUS-26) or a 2,2′-bipyrimidine derivative bearing two 5-hexyl-2,2′-bithiophene units at the 5,5′-positions (TUS-27) have been synthesized for application in dye-sensitized solar cells. TUS-27 shows a strong absorption at around 460 nm, mainly attributed to a π-π* transition in the 5,5′-disubstituted 2,2′-bipyrimidine ligand, and an onset wavelength of the absorption spectrum that is redshifted by about 50 nm relative to those of structurally analogous sensitizers (cis-[Ru(dcbpy)(bpy)(NCS)2] and N719). The energy level of the LUMO of TUS-27 is relatively close to that of the conduction band of TiO2. Dye-sensitized solar cells containing TUS-26 and TUS-27 showed much poorer performances than those containing cis-[Ru(dcbpy)(bpy)(NCS)2] and N719, even though an electrolyte containing no 4-tert-butylpyridine was used to adjust the energy of the conduction band of TiO2. The results of DFT calculations indicated that both unfavorable populations of LUMO and LUMO+1, and the lower energy level of LUMO+1, contribute to the much poorer solar cell performances of the TUS sensitizers. In addition, photovoltaic measurements also suggested that enhancement of backward electron transfer from the conduction band of TiO 2 to the one-electron-oxidized form of the dye or to I 3 - in the electrolyte is another reason for the inferior performances of the TUS sensitizers. Two novel ruthenium sensitizers with a 2,2′-bipyrimidine (TUS-26) or a 2,2′-bipyrimidine derivative bearing two 5-hexyl-2,2′-bithiophene units at the 5,5′-positions (TUS-27) have been synthesized. The performances of these sensitizers in dye-sensitized solar cells have been investigated.",
author = "Hironobu Ozawa and Hiroki Kawaguchi and Yu Okuyama and Hironori Arakawa",
year = "2013",
month = "10",
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T1 - Ruthenium sensitizers with 2,2′-bipyrimidine or a 5,5′-disubstituted 2,2′-bipyrimidine ligand

T2 - Synthesis, photo- and electrochemical properties, and application to dye-sensitized solar cells

AU - Ozawa, Hironobu

AU - Kawaguchi, Hiroki

AU - Okuyama, Yu

AU - Arakawa, Hironori

PY - 2013/10/1

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N2 - Novel ruthenium sensitizers with 2,2′-bipyrimidine (TUS-26) or a 2,2′-bipyrimidine derivative bearing two 5-hexyl-2,2′-bithiophene units at the 5,5′-positions (TUS-27) have been synthesized for application in dye-sensitized solar cells. TUS-27 shows a strong absorption at around 460 nm, mainly attributed to a π-π* transition in the 5,5′-disubstituted 2,2′-bipyrimidine ligand, and an onset wavelength of the absorption spectrum that is redshifted by about 50 nm relative to those of structurally analogous sensitizers (cis-[Ru(dcbpy)(bpy)(NCS)2] and N719). The energy level of the LUMO of TUS-27 is relatively close to that of the conduction band of TiO2. Dye-sensitized solar cells containing TUS-26 and TUS-27 showed much poorer performances than those containing cis-[Ru(dcbpy)(bpy)(NCS)2] and N719, even though an electrolyte containing no 4-tert-butylpyridine was used to adjust the energy of the conduction band of TiO2. The results of DFT calculations indicated that both unfavorable populations of LUMO and LUMO+1, and the lower energy level of LUMO+1, contribute to the much poorer solar cell performances of the TUS sensitizers. In addition, photovoltaic measurements also suggested that enhancement of backward electron transfer from the conduction band of TiO 2 to the one-electron-oxidized form of the dye or to I 3 - in the electrolyte is another reason for the inferior performances of the TUS sensitizers. Two novel ruthenium sensitizers with a 2,2′-bipyrimidine (TUS-26) or a 2,2′-bipyrimidine derivative bearing two 5-hexyl-2,2′-bithiophene units at the 5,5′-positions (TUS-27) have been synthesized. The performances of these sensitizers in dye-sensitized solar cells have been investigated.

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