A Molecular Tetrad That Generates a High-Energy Charge-Separated State by Mimicking the Photosynthetic Z-Scheme
| Autor: | Erik Göransson, Abhinandan Makhal, Jonas Petersson, Ludovic Favereau, Yann Pellegrin, Fabrice Odobel, Errol Blart, Leif Hammarström |
|---|---|
| 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, Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
Boron Compounds
Quantum yield Electron donor Diamines 010402 general chemistry Photosynthesis Photochemistry Photosystem I 01 natural sciences 7. Clean energy Biochemistry Catalysis Ruthenium chemistry.chemical_compound Colloid and Surface Chemistry Biomimetic Materials Coordination Complexes Tetrad ComputingMilieux_MISCELLANEOUS Photosystem chemistry.chemical_classification Photosystem I Protein Complex 010405 organic chemistry [CHIM.ORGA]Chemical Sciences/Organic chemistry Photoelectron Spectroscopy Photosystem II Protein Complex General Chemistry Electron acceptor Plants Photochemical Processes 0104 chemical sciences chemistry BODIPY |
| Zdroj: | Journal of the American Chemical Society Journal of the American Chemical Society, American Chemical Society, 2016, 138 (11), pp.3752-3760. ⟨10.1021/jacs.5b12650⟩ Journal of the American Chemical Society, 2016, 138 (11), pp.3752-3760. ⟨10.1021/jacs.5b12650⟩ |
| ISSN: | 0002-7863 1520-5126 |
| DOI: | 10.1021/jacs.5b12650⟩ |
| Popis: | The oxygenic photosynthesis of green plants, green algae, and cyanobacteria is the major provider of energy-rich compounds in the biosphere. The so-called "Z-scheme" is at the heart of this "engine of life". Two photosystems (photosystem I and II) work in series to build up a higher redox ability than each photosystem alone can provide, which is necessary to drive water oxidation into oxygen and NADP(+) reduction into NADPH with visible light. Here we show a mimic of the Z-scheme with a molecular tetrad. The tetrad Bodipy-NDI-TAPD-Ru is composed of two different dyes-4,4-difluoro-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene (Bodipy) and a Ru(II)(bipyridine)3 (Ru) derivative-which are connected to a naphthalene diimide (NDI) electron acceptor and tetraalkylphenyldiamine (TAPD) playing the role of electron donor. A strong laser pulse excitation of visible light where the two dye molecules (Ru and Bodipy) absorb with equal probability leads to the cooperative formation of a highly energetic charge-separated state composed of an oxidized Bodipy and a reduced Ru. The latter state cannot be reached by one single-photon absorption. The energy of the final charge-separated state (oxidized Bodipy/reduced Ru) in the tetrad lies higher than that in the reference dyads (Bodipy-NDI and TAPD-Ru), leading to the energy efficiency of the tetrad being 47% of the sum of the photon threshold energies. Its lifetime was increased by several orders of magnitude compared to that in the reference dyads Bodipy-NDI and TAPD-Ru, as it passes from about 3 ns in each dyad to 850 ns in the tetrad. The overall quantum yield formation of this extended charge-separated state is estimated to be 24%. Our proof-of-concept result demonstrates the capability to translate a crucial photosynthetic energy conversion principle into man-made molecular systems for solar fuel formation, to obtain products of higher energy content than those produced by a single photon absorption. |
| Databáze: | OpenAIRE |
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