Institut de Chimie Moléculaire et des Matériaux d'Orsay

Chimie Inorganique

Artifical photosynthesis

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

Postdoc : Dr. Daiann Sosa-Carrizo, Dr. Sandeep Kumar

PhD students : Eva Pugliese, Haroon Rashid, Adrien Smith, Ronging Lin

Associate researchers (I2BC, CEA Saclay) :  Dr. Winfried Leibl, Dr. Philipp Gotico


Axis 1 : Photoinduced electron transfer (A. Aukauloo)

Axis 2 : Catalytic reduction of CO2 and H2 production for energy (Z. Halime)

Axis 3 : Catalytic oxidation reactions (M. Sircoglou / Z. Halime)

Axis 4 : Computational studies of intermediates and reaction mechanisms (M. Sircoglou)

 

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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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)

  • ANR Européenne IMPULSE (2023-2026)
  • LABEX Charmmmat 2023, Postdoc
  • PERR CO2-Panchromatic (2023-2028)
  • ANR ALCA-N (2021-2025)
  • LABEX Charmmmat 2021, Post-doc —BDE et Amination C(sp3)-H : peut-on bafouer l’ordre naturel de réactivité ?
  • ANR LOCO (2019-2023)
  • 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

Ongoing

Rongning Lin — Molecular catalysts for water activation and oxidation

PhD advisor : Ally Aukauloo ; Co-advisor : Zakaria Halime (Started in september 2022)


Haroon Rashid — Polymeric porphyrin based materials for the activation and reduction of CO2

PhD advisor : Ally Aukauloo ; Co-advisor : Winfried Leibl (CEA) (Started in december 2021)


Adrien Smith — Activation and reduction of CO2 by molecular complexes based on metallo-porphyrins

PhD advisor : Ally Aukauloo ; Co-advisor : Zakaria Halime (Started in september 2021)


Eva Pugliese — Photoinduced reduction of CO2 and mechanistic study

PhD advisor : Ally Aukauloo ; Co-advisor : Zakaria Halime (Started in october 2020)


Defended

Chanjuan Zhang —Heterogeneous CO₂ electroreduction by macrocyclic molecular catalysts (2023)

PhD advisor : Ally Aukauloo ; Co-advisor : Zakaria Halime


Adelais Trapali — Synthesis and characterization of new porphyrin-based derivatives for CO2 and O2 reduction (2022)

PhD advisor : Ally Aukauloo ; Co-advisor : Coutsolelos Thanassis (Univ. of Crete) (Started in october 2019)


Asma KhadhraouiDevelopment of new molecular catalysts for CO2 reduction (2022)

PhD advisor : Ally Aukauloo ; Co-advisor : Zakaria Halime


Nhat Tam Vo — Complexe de fer(III) semi-hémique bioinspiré pour les réactions chimiques et photochimiques de transfert d'atome d'oxygène (2019)

Directeur de thèse : Ally Aukauloo ; Co-encadrante : Marie Sircoglou


Philipp GoticoStratégies bio-inspirées pour la réduction catalytique et la valorisation du dioxyde de carbone (2019)

Directeur de thèse : Winfried Leibl  (CEA) ; Co-directeur : Ally Aukauloo


Youngju RoComplexes moléculaires pour la photosynthèse artificielle (2019)

Directeur de thèse : Ally Aukauloo


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.


Second Coordination Sphere Effect Shifts CO2 to CO Reduction by Iron Porphyrin from Fe0 to FeI. S. Amanullah, P. Gotico, M. Sircoglou, W. Leibl, M. J. Llansola-Portoles, T. Tibiletti, A. Quaranta, Z. Halime, A. Aukauloo, Angewandte Chemie International Edition, 2024, 63, e202314439

Rhodium(II)-Catalyzed Selective C(sp3)−H Amination of Alkanes. V. Boquet, J. A. Guimaraes Naves, E. Brunard, A. Nasrallah, M. Joigneaux, E. D. Sosa Carrizo, T. Saget, B. Darses, M. Sircoglou, P. Dauban, European Journal of Organic Chemistry, 2023, 26, e202300352

Unlocking full and fast conversion in photocatalytic carbon dioxide reduction for applications in radio-carbonylation. S. Monticelli, A. Talbot, P. Gotico, F. Caillé, O. Loreau, A. Del Vecchio, A. Malandain, A. Sallustrau, W. Leibl, A. Aukauloo, F. Taran, Z. Halime, D. Audisio, Nature Communications, 2023, 14, 4451

Bimetallic Molecular Catalyst Design for Carbon Dioxide Reduction. P. Gotico, Z. Halime, W. Leibl, A. Aukauloo, ChemPlusChem, 2023, 88, e202300222

Divergent Behavior in the Chemistry of Metal-Bis(dithiolene) Complexes Appended with Peripheral Aliphatic Butyl Chains. E. Prignot, C. Zhang, O. Jeannin, Z. Halime, R. Gramage-Doria, F. Camerel, European Journal of Inorganic Chemistry, 2023, 26, e202200591

Efficient Hydrogen Production at pH 7 in Water with a Heterogeneous Electrocatalyst Based on a Neutral Dimeric Cobalt-Dithiolene Complex. C. Zhang, E. Prignot, O. Jeannin, A. Vacher, D. Dragoe, F. Camerel, Z. Halime, R. Gramage-Doria, ACS Catal., 2023, 13, 2367-2373

Bio-Inspired Bimetallic Cooperativity Through a Hydrogen Bonding Spacer in CO2 Reduction. C. Zhang, P. Gotico, R. Guillot, D. Dragoe, W. Leibl, Z. Halime, A. Aukauloo, Angewandte Chemie International Edition, 2023, 62, e202214665

Photocatalytic generation of a non-heme Fe(iii)-hydroperoxo species with O2 in water for the oxygen atom transfer reaction. E. Pugliese, N. T. Vo, A. Boussac, F. Banse, Y. Mekmouche, J. Simaan, T. Tron, P. Gotico, M. Sircoglou, Z. Halime, W. Leibl, A. Aukauloo, Chem. Sci., 2022, 13, 12332-12339

Photocatalytic Hydrogen Production and Carbon Dioxide Reduction Catalyzed by an Artificial Cobalt Hemoprotein. G. A. O. Udry, L. Tiessler-Sala, E. Pugliese, A. Urvoas, Z. Halime, J.-D. Maréchal, J.-P. Mahy, R. Ricoux, Int. J. Mol. Sci., 2022, 23, 14640

Rhodium(II)-Catalyzed Enantioselective Intermolecular Aziridination of Alkenes. V. Boquet, A. Nasrallah, A. L. Dana, E. Brunard, P. H. Di Chenna, F. J. Duran, P. Retailleau, B. Darses, M. Sircoglou, P. Dauban, J. Am. Chem. Soc., 2022, 144, 17156-17164

Dissection of Light-Induced Charge Accumulation at a Highly Active Iron Porphyrin: Insights in the Photocatalytic CO2 Reduction. E. Pugliese, P. Gotico, I. Wehrung, B. Boitrel, A. Quaranta, M.-H. Ha-Thi, T. Pino, M. Sircoglou, W. Leibl, Z. Halime, A. Aukauloo, Angewandte Chemie International Edition, 2022, 61, e202117530

Proton-controlled Action of an Imidazole as Electron Relay in a Photoredox Triad. P. Gotico, C. Herrero, S. Protti, A. Quaranta, S. Sheth, R. Fallahpour, R. Farran, Z. Halime, M. Sircoglou, A. Aukauloo, W. Leibl, Photochemical & Photobiological Sciences, 2022, 21, 247-259

Shaping the Electrocatalytic Performance of Metal Complexes for CO2 Reduction. P. Gotico, W. Leibl, Z. Halime, A. Aukauloo, ChemElectroChem, 2021, 8, 3472-3481

Intercepting a transient non-hemic pyridine N-oxide Fe(iii) species involved in OAT reactions. N. T. Vo, C. Herrero, R. Guillot, T. Inceoglu, W. Leibl, M. Clémancey, P. Dubourdeaux, G. Blondin, A. Aukauloo, M. Sircoglou, Chem. Commun., 2021, 57, 12836-12839

Imbroglio at a photoredox-iron-porphyrin catalyst dyad for the photocatalytic CO2 reduction. A. Trapali, P. Gotico, C. Herrero, M.-H. Ha-Thi, T. Pino, W. Leibl, G. Charalambidis, C. Athanassios, Z. Halime, A. Aukauloo, Comptes Rendus Chimie, 2021, 1-14

Second-sphere hydrogen-bonding enhances heterogeneous electrocatalytic CO2 to CO reduction by iron porphyrins in water. C. Zhang, D. Dragoe, F. Brisset, B. Boitrel, B. Lassalle-Kaiser, W. Leibl, Z. Halime, A. Aukauloo, Green Chem., 2021, 23, 8979-8987

Tracking Charge Accumulation in a Functional Triazole-Linked Ruthenium-Rhenium Dyad Towards Photocatalytic Carbon Dioxide Reduction. P. Gotico, T.-T. Tran, A. Baron, B. Vauzeilles, C. Lefumeux, M.-H. Ha-Thi, T. Pino, Z. Halime, A. Quaranta, W. Leibl, A. Aukauloo, ChemPhotoChem, 2021, 5, 654-664

Enhanced Photoinduced Electron Transfer Through a Tyrosine Relay in a De Novo Designed Protein Scaffold Bearing a Photoredox Unit and a FeIIS4 Site. A. Tebo, A. Quaranta, V. L. Pecoraro, A. Aukauloo, ChemPhotoChem, 2021, 5, 665-668

Ligand Radical Mediated Water Oxidation by a Family of Copper o-Phenylene Bis-oxamidate Complexes. S. Chattopadhyay, A. Ghatak, Y. Ro, R. Guillot, Z. Halime, A. Aukauloo, A. Dey, Inorg. Chem., 2021, 60, 9442-9455

Tracking light-induced electron transfer toward O2 in a hybrid photoredox-laccase system. R. Farran, Y. Mekmouche, N. T. Vo, C. Herrero, A. Quaranta, M. Sircoglou, F. Banse, P. Rousselot-Pailley, A. J. Simaan, A. Aukauloo, T. Tron, W. Leibl, iScience, 2021, 24, 102378

Phthalocyanine as a Bioinspired Model for Chlorophyll f-Containing Photosystem II Drives Photosynthesis into the Far-Red Region. J. Follana-Berná, R. Farran, W. Leibl, A. Quaranta, Á. Sastre-Santos, A. Aukauloo, Angewandte Chemie International Edition, 2021, 60, 12284-12288

Through-Space Electrostatic Interactions Surpass Classical Through-Bond Electronic Effects in Enhancing CO2 Reduction Performance of Iron Porphyrins. A. Khadhraoui, P. Gotico, W. Leibl, Z. Halime, A. Aukauloo, ChemSusChem, 2021, 14, 1308-1315

Efficient light activation of a [Ru(bpy)(tpy)Cl]+ catalyst by a porphyrin photosensitizer at small driving force. G. Charalambidis, A. Charisiadis, S. Margiola, A. Coutsolelos, A. Aukauloo, W. Leibl, A. Quaranta, Polyhedron, 2020, 190, 114775

Recent advances in metalloporphyrin-based catalyst design towards carbon dioxide reduction: from bio-inspired second coordination sphere modifications to hierarchical architectures. P. Gotico, Z. Halime, A. Aukauloo, Dalton Trans., 2020, 49, 2381-2396

Atropisomeric Hydrogen Bonding Control for CO2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins. P. Gotico, L. Roupnel, R. Guillot, M. Sircoglou, W. Leibl, Z. Halime, A. Aukauloo, Angewandte Chemie International Edition, 2020, 59, 22451-22455

Visible light-driven simultaneous water oxidation and quinone reduction by a nano-structured conjugated polymer without co-catalysts. J. Patel, X. Yuan, S. M. Marinho, W. Leibl, H. Remita, A. Aukauloo, Chem. Sci., 2020

Spectroscopic Characterisation of a Bio-Inspired Ni-Based Proton Reduction Catalyst Bearing a Pentadentate N2S3 Ligand with Improved Photocatalytic Activity. P. Gotico, D. Moonshiram, C. Liu, X. Zhang, R. Guillot, A. Quaranta, Z. Halime, W. Leibl, A. Aukauloo, Chemistry – A European Journal, 2020, 26, 2859 – 2868

Time-resolved X-ray absorption spectroelectrochemistry of redox active species in solution. K. Cheaib, B. Maurice, T. Mateo, Z. Halime, B. Lassalle-Kaiser, Journal of Synchrotron Radiation, 2019, 26, 1980-1985

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.

 

 


Last update on August 1st 2023