A Molecular Tetrad That Generates a High-Energy Charge-Separated State by Mimicking the Photosynthetic Z-Scheme

Ludovic Favereau, Abhinandan Makhal, Yann Pellegrin, Errol Blart, Jonas Petersson, Erik Göransson, Leif Hammarström, Fabrice Odobel

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

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 RuII(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.

Original languageEnglish
Pages (from-to)3752-3760
Number of pages9
JournalJournal of the American Chemical Society
Volume138
Issue number11
DOIs
Publication statusPublished - Mar 23 2016

Fingerprint

Naphthalene
Photons
NADP
Coloring Agents
Dyes
Electrons
Viridiplantae
Photosystem I Protein Complex
Light
Chlorophyta
Photosystem II Protein Complex
Photosynthesis
Cyanobacteria
Solar System
Quantum yield
Algae
Energy conversion
Oxidation-Reduction
Energy efficiency
Laser pulses

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Favereau, L., Makhal, A., Pellegrin, Y., Blart, E., Petersson, J., Göransson, E., ... Odobel, F. (2016). A Molecular Tetrad That Generates a High-Energy Charge-Separated State by Mimicking the Photosynthetic Z-Scheme. Journal of the American Chemical Society, 138(11), 3752-3760. https://doi.org/10.1021/jacs.5b12650

A Molecular Tetrad That Generates a High-Energy Charge-Separated State by Mimicking the Photosynthetic Z-Scheme. / Favereau, Ludovic; Makhal, Abhinandan; Pellegrin, Yann; Blart, Errol; Petersson, Jonas; Göransson, Erik; Hammarström, Leif; Odobel, Fabrice.

In: Journal of the American Chemical Society, Vol. 138, No. 11, 23.03.2016, p. 3752-3760.

Research output: Contribution to journalArticle

Favereau, Ludovic ; Makhal, Abhinandan ; Pellegrin, Yann ; Blart, Errol ; Petersson, Jonas ; Göransson, Erik ; Hammarström, Leif ; Odobel, Fabrice. / A Molecular Tetrad That Generates a High-Energy Charge-Separated State by Mimicking the Photosynthetic Z-Scheme. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 11. pp. 3752-3760.
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