The electronic structure of the cis-bis(4,4′-dicarboxy-2,2′-bipyridine)-bis(isothiocyanato)ruthenium(II) complex and its ligand 2,2′-bipyridyl-4,4′-dicarboxylic acid studied with electron spectroscopy

Rensmo, Håkan; Södergren, Sven; Patthey, L.; Westermark, Karin; Vayssières, Lionel; Kohle, Oliver; Brühwiler, Paul A.; Hagfeldt, Anders; Siegbahn, Hans

doi:10.1016/s0009-2614(97)00670-2

Cited by 81 publications

(64 citation statements)

References 18 publications

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“…The strong concentration of the HOMO on the central Ru atom and the thiocyanate ligands is consistent with previous experimental and theoretical studies. 18,19,23,24,32,36 In an intuitive picture, the photoinduced removal of an electron from the HOMO of the dye molecule is expected to lead to a significant increase in inner-shell binding energies in those parts of the molecule where most of the HOMO electron density is localized. This is consistent with our experimental finding that the excitation-induced chemical shift is much more prominent in the Ru 3d doublet than in the C 1s carboxyl and pyridine signals.…”

Section: 23−26mentioning

confidence: 99%

Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye–Semiconductor Interface

Siefermann

Pemmaraju

Neppl

et al. 2014

J. Phys. Chem. Lett.

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Understanding interfacial charge-transfer processes on the atomic level is crucial to support the rational design of energy-challenge relevant systems such as solar cells, batteries, and photocatalysts. A femtosecond time-resolved core-level photoelectron spectroscopy study is performed that probes the electronic structure of the interface between ruthenium-based N3 dye molecules and ZnO nanocrystals within the first picosecond after photoexcitation and from the unique perspective of the Ru reporter atom at the center of the dye. A transient chemical shift of the Ru 3d inner-shell photolines by (2.3 ± 0.2) eV to higher binding energies is observed 500 fs after photoexcitation of the dye. The experimental results are interpreted with the aid of ab initio calculations using constrained density functional theory. Strong indications for the formation of an interfacial charge-transfer state are presented, providing direct insight into a transient electronic configuration that may limit the efficiency of photoinduced free charge-carrier generation.

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Section: 23−26mentioning

confidence: 99%

Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye–Semiconductor Interface

Siefermann

Pemmaraju

Neppl

et al. 2014

J. Phys. Chem. Lett.

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“…Previously, theoretical investigations on ruthenium photosensitizers have mainly been performed by means of semiempirical, [25][26][27][28] density functional theory (DFT), [29] and time-dependent DFT (TDDFT) [30][31][32][33][34][35] calculations. Here, we use semiempirical computations with ZINDO/1 to calculate the electronic structure and the localization of the frontier orbitals of N3, CYC-P1, and CYC-P2.…”

Section: Full Papermentioning

confidence: 99%

New Ruthenium Complexes Containing Oligoalkylthiophene‐Substituted 1,10‐Phenanthroline for Nanocrystalline Dye‐Sensitized Solar Cells

Chen

et al. 2006

Adv Funct Materials

116

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Two new ruthenium complexes [Ru(dcbpy)(L)(NCS)2], where dcbpy is 4,4′‐dicarboxylic acid‐2,2′‐bipyridine and L is 3,8‐bis(4‐octylthiophen‐2‐yl)‐1,10‐phenanthroline (CYC‐P1) or 3,8‐bis(4‐octyl‐5‐(4‐octylthiophen‐2‐yl)thiophen‐2‐yl)‐1,10‐phenanthroline (CYC‐P2), are synthesized, characterized by physicochemical and semiempirical computational methods, and used as photosensitizers in nanocrystalline dye‐sensitized solar cells. It was found that the difference in light‐harvesting ability between CYC‐P1 and CYC‐P2 is associated mainly with the location of the frontier orbitals, in particular the highest occupied molecular orbital (HOMO). Increasing the conjugation length of the ancillary ligand decreases the energy of the metal‐to‐ligand charge transfer (MLCT) transition, but at the same time reduces the molar absorption coefficient, owing to the HOMO located partially on the ancillary ligand of the ruthenium complex. The incident photon‐to‐current conversion efficiency curves of the devices are consistent with the MLCT band of the complexes. Therefore, the overall efficiencies of CYC‐P1 and CYC‐P2 sensitized cells are 6.01 and 3.42 %, respectively, compared to a cis‐di(thiocyanato)‐bis(2,2′‐bipyridyl)‐4,4′‐dicarboxylate ruthenium(II)‐sensitized device, which is 7.70 % using the same device‐fabrication process and measuring parameters.

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“…Among the known sensitizers, the performance of the cis-RuL 2 (SCN) 2 was found to be outstanding. [3][4][5] Most of the synthetic methods use 4-methylpyridine as the starting materials. Firstly, 2-halo-pyridine was synthesized from 4-methylpyridine through electrophilic substitution.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Energy Conversion Efficiency of La³⁺‐Modified Nanoporous TiO₂ Electrode Sensitized with a Ruthenium Complex

Wang

Guo

et al. 2008

Chin. J. Chem.

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The nature of TiO 2 films and sensitizer play significant roles in determining the overall efficiency and mechanical stability of dye sensitized solar cell. In this study, cis-RuL 2 (SCN) 2 , (L＝2,2'-dipyridine-4,4'-dicarboxlic acid) was synthesized from 4-methylpyridine by the procedure of cross-coupling, oxidation, conjugation and ligand substitution. TiO 2 films were obtained by blending P25 and TiO 2 sol. To increase the photoelectric properties of the thin TiO 2 films, La(NO 3 ) 3 with different concentrations (0.1%, 0.3%, 0.5% and 0.7%) were added into the sol. Both undoped and doped samples of the thin films were sensitized by cis-RuL 2 (SCN) 2 and structurally characterized by X-ray diffraction, atomic force microscopy and X-ray photoelectron spectroscopy. In addition, the photoelectric properties of the TiO 2 electrodes were investigated. The results show that doping lanthanum ions made the grain size smaller and surface area larger. When the concentration dopant is 0.5%, the short circuit current and open circuit voltage of the TiO 2 film reach maximum. The short circuit current increases 0.54 mA/cm 2 more than that of undoped film, and the open-circuit voltage increases 30.41 mV more than that of undoped film.

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The electronic structure of the cis-bis(4,4′-dicarboxy-2,2′-bipyridine)-bis(isothiocyanato)ruthenium(II) complex and its ligand 2,2′-bipyridyl-4,4′-dicarboxylic acid studied with electron spectroscopy

Cited by 81 publications

References 18 publications

Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye–Semiconductor Interface

Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye–Semiconductor Interface

New Ruthenium Complexes Containing Oligoalkylthiophene‐Substituted 1,10‐Phenanthroline for Nanocrystalline Dye‐Sensitized Solar Cells

Enhanced Energy Conversion Efficiency of La³⁺‐Modified Nanoporous TiO₂ Electrode Sensitized with a Ruthenium Complex

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The electronic structure of the cis-bis(4,4′-dicarboxy-2,2′-bipyridine)-bis(isothiocyanato)ruthenium(II) complex and its ligand 2,2′-bipyridyl-4,4′-dicarboxylic acid studied with electron spectroscopy

Cited by 81 publications

References 18 publications

Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye–Semiconductor Interface

Atomic-Scale Perspective of Ultrafast Charge Transfer at a Dye–Semiconductor Interface

New Ruthenium Complexes Containing Oligoalkylthiophene‐Substituted 1,10‐Phenanthroline for Nanocrystalline Dye‐Sensitized Solar Cells

Enhanced Energy Conversion Efficiency of La3+‐Modified Nanoporous TiO2 Electrode Sensitized with a Ruthenium Complex

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Enhanced Energy Conversion Efficiency of La³⁺‐Modified Nanoporous TiO₂ Electrode Sensitized with a Ruthenium Complex