Tris-bipyridine based dinuclear ruthenium(II)−osmium(III) complex dyads grafted onto TiO2 nanoparticles for mimicking the artificial photosynthetic Z-scheme
| Autor: | Fabrice Odobel, Abhinandan Makhal, Ludovic Favereau, Yann Pellegrin, Leif Hammarström, Erik Göransson, Errol Blart, David Provost |
|---|---|
| Přispěvatelé: | Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Angström Laboratory, Uppsala University, Knut och Alice Wallenbergs Stiftelse, MolecularZScheme ANR-13-BS07-0016-01, Agence Nationale de la Recherche |
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
General Physics and Astronomy chemistry.chemical_element 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 7. Clean energy 01 natural sciences 0104 chemical sciences Ruthenium Electron transfer Bipyridine chemistry.chemical_compound Dicarboxylic acid chemistry Covalent bond Excited state Ultrafast laser spectroscopy [CHIM]Chemical Sciences Osmium Physical and Theoretical Chemistry 0210 nano-technology ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2017, 19 (6), pp.4778-4786. ⟨10.1039/c6cp06679h⟩ |
| ISSN: | 1463-9076 1463-9084 |
| DOI: | 10.1039/c6cp06679h⟩ |
| Popis: | The Z-Scheme function within molecular systems has been rarely reported for solar energy conversion although it offers the possibility to achieve higher efficiency than single photon absorber photosystems due to the use of a wider range of visible light. In this study, we synthesized and investigated the electrochemical and spectroscopic properties of two new dyads based on ruthenium and osmium tris-bipyridine complexes covalently linked via a butane bridge to explore their ability to realize the Z-scheme function once immobilized on TiO2. These dyads can be grafted onto a nanocrystalline TiO2 film via the osmium complex bearing two dicarboxylic acid bipyridine ligands, while the ruthenium complex contains either two unsubstituted bipyridine ancillary ligands (RuH–Os) or two (4,4′-bis-trifluoromethyl-bipyridine) ancillary ligands (RuCF3–Os). Transient absorption spectroscopy studies of the Ru(II)–Os(III) dyads with femtosecond and nanosecond lasers were conducted both in solution and on TiO2. For both conditions, the photophysical studies revealed that the MLCT excited state of the ruthenium complex is strongly quenched and predominantly decays by energy transfer to the LMCT of the adjacent Os(III) complex, in spite of the high driving force for electron transfer. This unexpected result, which is in sharp contrast to previously reported Ru(II)–Os(III) dyads, precluded us to achieve the expected Z-scheme function. However, the above results may be a guide for designing new artificial molecular systems reproducing the complex function of a Z-scheme with molecular systems grafted onto a TiO2 mesoporous film. |
| Databáze: | OpenAIRE |
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