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In situ spectroelectrochemical and theoretical study on the oxidation of a 4H-imidazole-ruthenium dye adsorbed on nanocrystalline TiO2thin film electrodes
Abstract
Terpyridine 4H-imidazole-ruthenium(ii) complexes are considered promising candidates for use as sensitizers in dye sensitized solar cells (DSSCs) by displaying broad absorption in the visible range, where the dominant absorption features are due to metal-to-ligand charge transfer (MLCT) transitions. The ruthenium(iii) intermediates resulting from photoinduced MLCT transitions are essential intermediates in the photoredox-cycle of the DSSC. However, their photophysics is much less studied compared to the ruthenium(ii) parent systems. To this end, the structural alterations accompanying one-electron oxidation of the RuIm dye series (including a non-carboxylic RuIm precursor, and, carboxylic RuImCOO in solution and anchored to a nanocrystalline TiO2 film) are investigated via in situ experimental and theoretical UV-Vis absorption and resonance Raman (RR) spectroelectrochemistry. The excellent agreement between the experimental and the TDDFT spectra derived in this work allows for an in-depth assignment of UV-Vis and RR spectral features of the dyes. A concordant pronounced wavelength dependence with respect to the charge transfer character has been observed for the model system RuIm, and both RuImCOO in solution and attached on the TiO2 surface. Excitation at long wavelengths leads to the population of ligand-to-metal charge transfer states, i.e. photoreduction of the central ruthenium(iii) ion, while high-energy excitation features an intra-ligand charge transfer state localized on the 4H-imidazole moiety. Therefore, these 4H-imidazole ruthenium complexes investigated here are potential multi-photoelectron donors. One electron is donated from MLCT states, and additionally, the 4H-imidazole ligand reveals electron-donating character with a significant contribution to the excited states of the ruthenium(iii) complexes upon blue-light irradiation.
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Authors (8)
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Ying Zhang
- University Jena Institute of Physical Chemistry
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Stephan Kupfer
- University Jena Institute of Physical Chemistry
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Linda Zedler
- University Jena Institute of Physical Chemistry
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Julian Schindler
- University Jena Institute of Physical Chemistry
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Thomas Bocklitz
- University Jena Institute of Physical Chemistry
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Sven Rau
- University Ulm Institute of Inorganic Chemistry
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Benjamin Dietzek
- University Jena Institute of Physical Chemistry
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- Accepted or Published Version
- DOI:
- Digital Object Identifier (open in new tab) 10.1039/c5cp04484g
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Details
- Category:
- Articles
- Type:
- artykuł w czasopiśmie wyróżnionym w JCR
- Published in:
-
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
no. 17,
edition 44,
pages 29637 - 29646,
ISSN: 1463-9076 - Language:
- English
- Publication year:
- 2015
- Bibliographic description:
- Zhang Y., Kupfer S., Zedler L., Schindler J., Bocklitz T., Guthmuller J., Rau S., Dietzek B.: In situ spectroelectrochemical and theoretical study on the oxidation of a 4H-imidazole-ruthenium dye adsorbed on nanocrystalline TiO2thin film electrodes// PHYSICAL CHEMISTRY CHEMICAL PHYSICS. -Vol. 17, iss. 44 (2015), s.29637-29646
- DOI:
- Digital Object Identifier (open in new tab) 10.1039/c5cp04484g
- Verified by:
- Gdańsk University of Technology
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