Institut de Chimie Moléculaire et des Matériaux d'Orsay

Chimie Inorganique

Artifical photosynthesis

Ally Aukauloo (Prof), Marie Sircoglou (Associate Prof.), Zakaria Halime (Researcher)

Postdocs : Dr. Tania Tibiletti, Dr. Maria Castellano

PhD students : Naht Tam Vo, Philip Gottico, Asma Khadhraoui, Youngiu Ro

Associate researchers (I2BC, CEA Saclay) :  Dr. Winfried Leibl, Dr. Annamaria Quaranta


From Natural …

A stunning process in biology is how nature captures sunlight to make dioxygen from water thereby liberating the electrons and protons to reduce carbon dioxide in form of sugars. This process sustains oxygenic life on earth and it stands as the source of inspiration for chemists to use sunlight to transform the ever-increasing anthropogenic CO2 to a fuel using water as a renewable source of electrons and protons. The million-dollar question then is: can we manage to steal Nature’s secrets and perform better than Her?

H2O + 4 hν → O2 + 4 H+ + 4 e-

n CO2 + 2n e- + 2n H+ → (CH2O)n + n/2 O2

 

…to Artificial Photosynthesis

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Implementing the main functionalities of natural photosynthesis in synthetic modular assemblies is the defining target of molecular chemists. Our quests are to provide designed chemical models to support mechanistic proposals of enzymes implicated in transduction pathways of energy and ultimately to replicate their functions in robust and cost-effective systems on a grand scale

In the artifical photosynthesis group, we follow three main thrusts :

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Axis 1 : Photoinduced electron transfer

Axis 2 : Oxidation chemistry

Axis 3 : Reduction reactions

 

Keywords

Photoinduced electron transfer / Bioinspired catalysts / Water oxidation / CO2 reduction / H2 production / Transition metals / Chromophore / Proton coupled electron transfer / Mechanism / Structure-property relationship / Non-innocent ligands / Porphyrin / Electronic properties / Spin / Small molecules activation / Trapping of intermediates / Artificial photosynthesis / Renewable energies / Sustainability

Techniques

Organic synthesis / Catalysis / Inorganic chemistry / Electrochemistry / EPR / UV-vis spectroscopy / Stopped Flow / Theoretical Calculations / Photophysics


Collaborations

- T. Tron, J. Simaan, Y. Meckmouche, M. Orio (Ism2, Marseille)

- F. Banse, K. Sénéchal-David (ICMMO, Orsay)

- D. Audisio (LMC-CEA, Gif-sur-Yvette)

- Dooshaye Moonshiram (Argonne National Laboratory)

- T. Coutsolelos (University of Heraklion, Crete)

 

- P. Dauban (ICSN, Orsay)

- B. Boitrel (ISCR-OMC, Rennes)

- H. Remita (LCP, Orsay)

- M.-H. Ha-Thi, T. Pino (ISMO, Orsay)

- B. Lassale (SOLEIL, Gif-sur-Yvette)

  • LABEX Charmmmat 2018, Post-doc : Towards Photo-Activated Catalytic C-H Amination Processes
  • LABEX Charmmmat 2018, Post-doc : Complexe hétérobimétallique bioinspiré pour la réduction du CO2 : synthèse, électrochimie et spectroscopie
  • LABEX Charmmmat 2017, Chaire, Invité Pr. Lionel Cheruzel de l’Université San José Californie
  • Initiatives de Recherches Stratégiques (IRS- Paris Saclay), MOMENTOM regroupant 26 équipes de recherches (2017-2020)
  • LABEX Charmmmat 2017, Equipement et plateforme : Acquisition d’un spectromètre UV-Vis Cary60 combiné avec un cryostat CoolSpek UV
  • ANR Multielectronic light driven water activation for oxygen atom transfer reactions under mild conditions. Coordinateur T. Tron (Aix Marseille Université), Partenaire (2015-2019), 1 thèse, 2 post-doc
  • LABEX Charmmmat 2014, Postdoc: Photoactivation pour l’Amination C(sp3)-H catalysée au Fer
  • IDEX Solar Fuel 2014-2017, Thèse IDEX S. Mendes
  • Attractivité 2012 : Acquisition Potentiostat Autolab 204N
  • Chateaubriand Ambassade de France USA 2013, Alison Tebo, University of Michigan PhD
  • PIE CNRS, COMMERCE H2, Réseaux de catalyseurs moléculaires pour la production de H2.2010-2012
  • SurPhox cNano Ile de France 2010
  • Blaise Pascal International Chair 2009-2011, Pr. Vince Pecoraro University of Michigan USA, Artificial Photosynthesis
  • ANR Blanc Take Care Transport et transfert couplés d'électron et de proton dans des systèmes biomimétiques, Coordinateur M. Robert (Université Paris Diderot) Partenaire 2010-2013
  • ANR Blanc TECHBIOHYP Vers des cellules bioinspirées efficaces et bon marché pour la production photoélectrochimique d'hydrogène. Coordinateur J-F.Cornet (Université C.Ferrand) Partenaire 2010-2014
  • Projet Européen SOLAR-H2, European Solar-Fuel Initiative- Renewable Hydrogen from Sun and Water. Science Linking Molecular Biomimetics and Genetics. (Leader Work Package 1, Coordinateur S. Styring, University of Uppsala 2008-2011)

PhD theses

On going

Youngju Ro — Light-induced water activation using sensitizer-catalyst dyads

PhD advisor : Ally Aukauloo (Started in june 2018)


Asma Khadhraoui — Development of new catalysts for the CO2 reduction

PhD advisor : Ally Aukauloo ; Co-advisor : Zakaria Halime (Started in october 2017)


Tam Vo — Electrochemical and photochemical water activation by 1st row molecular complexes. Relation between structure and reactivity of the metal-oxo species?

PhD advisor : Ally Aukauloo ; Co-advisor : Marie Sircoglou (Started in october 2016)


Philipp Gotico — Photocatalysis of Co2 reduction

PhD advisor : Winfried Leibl  (CEA) ; Co-advisor : Ally Aukauloo (Démarrée en septembre 2016)


Defended

Clémence DucloisetStudy of complexes for reactions by oxygen or nitrogen atom transfer : From synthesis to photoactivation (2017)

PhD advisor : Ally Aukauloo ; PhD advisor : Marie Sircoglou


Stéphanie Mendes-MarinhoCharacterization of the charge transfer mechanism in photocatalytic molecules, towards the energy production by artifical photosynthesis (2017)

PhD advisor : Ally Aukauloo


Stéphanie Cherdo From cage complexes to nanoparticles, new catalysts for hydrogen production (2013)

PhD advisor : Ally Aukauloo


Sujitraj ShethSynthesis and characterization of catalysts for photo-oxidation of water (2013)

PhD advisor : Ally Aukauloo ; Co-advisor : Winfried Leibl (CEA, Saclay)

Last publications (2015 - Today)

Our comprehensive list of publications can be found HERE.


A Reversible Electron Relay to Exclude Sacrificial Electron Donors in the Photocatalytic Oxygen Atom Transfer Reaction with O2 in Water. N. T. Vo, Y. Mekmouche, T. Tron, R. Guillot, F. Banse, Z. Halime, M. Sircoglou, W. Leibl, A. Aukauloo, Angewandte Chemie International Edition, 2019, 58, 16023-16027

Electronic and spin delocalization in a switchable trinuclear triphenylene trisemiquinone bridged Ni3 complex. Y. Wang, F. Lambert, E. Rivière, R. Guillot, C. Herrero, A. Tissot, Z. Halime, T. Mallah, Chem. Commun., 2019, 55, 12336-12339

Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO2 Reduction of Iron Porphyrins. P. Gotico, B. Boitrel, R. Guillot, M. Sircoglou, A. Quaranta, Z. Halime, W. Leibl, A. Aukauloo, Angewandte Chemie International Edition, 2019, 58, 4504-4509

Local ionic liquid environment at a modified iron porphyrin catalyst enhances the electrocatalytic performance of CO2 to CO reduction in water. A. Khadhraoui, P. Gotico, B. Boitrel, W. Leibl, Z. Halime, A. Aukauloo, Chem. Commun., 2018, 54, 11630-11633

Visible Light-Driven Reduction of CO2 to CO and Its Subsequent Valorization in Carbonylation Chemistry and 13C Isotope Labelling. P. Gotico, A. Del Vecchio, D. Audisio, A. Quaranta, Z. Halime, W. Leibl, A. Aukauloo, ChemPhotoChem, 2018, 2, 715-719

Water Molecules Gating a Photoinduced One Electron Two Protons Transfer in a Tyr/His model of Photosystem II. G. Chararalambidis, S. Das, A. Trapali, A. Quaranta, M. Orio, Z. Halime, P. Fertey, R. Guillot, C. Athanassios, W. Leibl, A. Aukauloo, M. Sircoglou, Angew. Chem. Int. Ed., 2018, 57, 9013-9017

Snapshots of Light Induced Accumulation of Two Charges on Methylviologen using a Sequential Nanosecond Pump–Pump Photoexcitation. T.-T. Tran, M.-H. Ha-Thi, T. Pino, A. Quaranta, C. Lefumeux, W. Leibl, A. Aukauloo, J. Phys. Chem. Lett., 2018, 9, 1086-1091

Light-Induced Activation of the Du Bois [RhII2(Esp)2] Catalyst for Nitrogen Atom Transfer Reactions. R. Farran, C. Ducloiset, J. Buendia, N. T. Vo, R. Guillot, Z. Halime, P. Dauban, W. Leibl, M. Sircoglou, A. Aukauloo, ChemPhotoChem, 2017, 1, 562-567

Time-Resolved Interception of Multiple-Charge Accumulation in a Sensitizer–Acceptor Dyad. S. Mendes marinho, M.-H. Ha-Thi, V.-T. Pham, A. Quaranta, T. Pino, C. Lefumeux, T. Chamaillé, W. Leibl, A. Aukauloo, Angewandte Chemie International Edition, 2017, 11, 15936–15940

Intramolecular Photogeneration of a Tyrosine Radical in a Designed Protein. A. G. Tebo, A. Quaranta, C. Herrero, V. L. Pecoraro, A. Aukauloo, ChemPhotoChem, 2017, 1, 89-92

Light-driven electron transfer in a modular assembly of a ruthenium(II) polypyridine sensitiser and a manganese(II) terpyridine unit separated by a redox active linkage. DFT analysis. A. G. Tebo, S. Das, R. Farran, C. Herrero, A. Quaranta, R. Fallahpour, S. Protti, M.-F. Charlot, A. Aukauloo, W. Leibl, Comptes Rendus Chimie, 2017, 20, 323-332

Elucidating the light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved x-ray absorption spectroscopy. D. Moonshiram, A. Picon, Á. Vázquez-Mayagoitia, X. Zhang, M.-F. Tu, P. Garrido-Barros, J.-P. Mahy, F. Avenier, A. Aukauloo, Chem. Commun., 2017, 53, 2725-2728

Monoanionic Dipyrrin–Pyridine Ligands: Synthesis, Structure and Photophysical Properties. C. Ducloiset, P. Jouin, E. Paredes, R. Guillot, M. Sircoglou, M. Orio, W. Leibl, A. Aukauloo, European Journal of Inorganic Chemistry, 2015, 2015, 5405-5410

Visible-Light-Driven Oxidation of Organic Substrates with Dioxygen Mediated by a [Ru(bpy)3]2+/Laccase System. L. Schneider, Y. Mekmouche, P. Rousselot-Pailley, A. J. Simaan, V. Robert, M. Réglier, A. Aukauloo, T. Tron, ChemSusChem, 2015, 8, 3048-3051

Redox Noninnocence of the Bridge in Copper(II) Salophen and Bis(oxamato) Complexes. D. De Bellefeuille, M. Orio, A.-L. Barra, A. Aukauloo, Y. Journaux, C. Philouze, X. Ottenwaelder, F. Thomas, Inorg. Chem., 2015, 54, 9013-9026

Synergistic "ping-pong" energy transfer for efficient light activation in a chromophore-catalyst dyad. A. Quaranta, G. Charalambidis, C. Herrero, S. Margiola, W. Leibl, A. Coutsolelos, A. Aukauloo, Phys. Chem. Chem. Phys., 2015, 17, 24166-24172

Ingénierie de la photosynthese artificielle. J.-F. Cornet, A. Aukauloo, F. Gloaguen, W. Leibl, L'actualité chimique, 2015, 397-398, 69-74

Successive light-induced two electron transfers in a Ru-Fe supramolecular assembly: from Ru-Fe(ii)-OH2 to Ru-Fe(iv)-oxo. C. Herrero, A. Quaranta, M. Sircoglou, K. Senechal-David, A. Baron, I. M. Marin, C. Buron, J.-P. Baltaze, W. Leibl, A. Aukauloo, F. Banse, Chem. Sci., 2015, 6, 2323-2327

Our group

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From left to right :
Philip Gottico, Zakaria Halime, Nhat Tam Vo, Tania Tibiletti, Winfried Leibl, Marie Sircoglou, Ally Aukauloo
Khaled Cheaib, Youngju Ro, Asma Khadhraoui, Annamaria Quaranta

The list of the former members of the group can be found HERE.