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14 results on '"Gros, Philippe C."'

1. Heteroleptic Pyridyl-Carbene Iron Complexes with Tuneable Electronic Properties

Author

Duchanois, Thibaut, Etienne, Thibaud, Beley, Marc, Assfeld, Xavier, Perpete, Eric A., Monari, Antonio, Gros, Philippe C., Structure et Réactivité des Systèmes Moléculaires Complexes (SRSMC), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Facultés Universitaires Notre Dame de la Paix (FUNDP), and Laboratoire de Chimie Théorique Appliquée

Subjects
Tridentate ligands, Absorption spectroscopy, Ligand, Iron, Substituent, Protonation, Photochemistry, Chromophores, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, N ligands, Photophysics, chemistry, Pyridine, Carbenes, [CHIM]Chemical Sciences, Terpyridine, Homoleptic, Carbene
Abstract

New heteroleptic iron complexes mixing a terpyridine bearing a protonable pyridyl substituent (pytpy) and a pyridyl carbene ligand (carb) have been prepared and characterised by UV/Vis spectroscopy, cyclic voltammetry and TD-DFT computations. The absorption spectrum of [Fe(carb)(pytpy)]2+ showed a notable redshift compared with the homoleptic [Fe(carb)2] 2+ complex. The MLCT transition occurred at even lower energy when the pendant pyridine was protonated, leading to a wide absorption domain in the 450-650 nm range. Calculations revealed the strong propensity of excited electrons to move from the metal to the pytpy ligand in the complex. This new family of complexes is a promising addition to the arsenal of iron-based chromophores with tuneable electronic properties.

Published
2014
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2. Impact of Polypyridyl Ru Complexes on Angiogenesis—Contribution to Their Antimetastatic Activity

Author

Ilona Gurgul, Olga Mazuryk, Kamila Stachyra, Rafał Olszanecki, Małgorzata Lekka, Michał Łomzik, Franck Suzenet, Philippe C. Gros, Małgorzata Brindell, Uniwersytet Jagielloński w Krakowie = Jagiellonian University (UJ), University of Lódź, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), This research was funded by the National Science Center in Poland for the OPUS Project No. 2016/21/B/NZ7/01081. I.G. acknowledges the support from InterDokMed project No. POWR.03.02.00-00-013/16. The APC was funded by the InterDokMed project No. POWR.03.02.00-00-013/16. F.S. acknowledges the support from Labex SynOrg (ANR-11-LABX-0029), Labex IRON (ANR-11-LABX-0018-01), the FEDER TECHSAB, the University of Orleans and the Centre-Val de Loire Region., and GROS, PHILIPPE C.

Subjects
[CHIM.THER] Chemical Sciences/Medicinal Chemistry, [SDV.CAN]Life Sciences [q-bio]/Cancer, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Ligands, migration, Ruthenium, Catalysis, Inorganic Chemistry, angiogenesis, 2,2'-Dipyridyl, polypyridyl ruthenium (II) complexes, [SDV.CAN] Life Sciences [q-bio]/Cancer, Coordination Complexes, Neoplasms, cell elasticity, Humans, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, endothelial cells, cell adhesion properties, cytotoxicity, focal adhesions, pseudovessel formation, Molecular Biology, Spectroscopy, Organic Chemistry, General Medicine, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Computer Science Applications, Phenanthrolines
Abstract

International audience; The use of polypyridyl Ru complexes to inhibit metastasis is a novel approach, and recent studies have shown promising results. We have reported recently that Ru (II) complexes gathering two 4,7-diphenyl-1,10-phenanthroline (dip) ligands and the one being 2,2′-bipyridine (bpy) or its derivative with a 4-[3-(2-nitro-1H-imidazol-1-yl)propyl (bpy-NitroIm) or 5-(4-{4′-methyl-[2,2′-bipyridine]-4-yl}but-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (bpy-SC) moieties can alter the metastatic cascade, among others, by modulating cell adhesion properties. In this work, we show further studies of this group of complexes by evaluating their effect on HMEC-1 endothelial cells. While all the tested complexes significantly inhibited the endothelial cell migration, Ru-bpy additionally interrupted the pseudovessels formation. Functional changes in endothelial cells might arise from the impact of the studied compounds on cell elasticity and expression of proteins (vinculin and paxillin) involved in focal adhesions. Furthermore, molecular studies showed that complexes modulate the expression of cell adhesion molecules, which has been suggested to be one of the factors that mediate the activation of angiogenesis. Based on the performed studies, we can conclude that the investigated polypyridyl Ru (II) complexes can deregulate the functionality of endothelial cells which may lead to the inhibition of angiogenesis.

Published
2022
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3. Bidentate pyridyl‐NHC ligands: synthesis, ground and excited state properties of their iron(II) complexes and role of the fac/mer isomerism

Author

Stefan Haacke, Antonio Francés-Monerris, Philippe C. Gros, Antonio Monari, Kévin Magra, Cristina Cebrian, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Facultat de Fisica [València] (UV), Universitat de València (UV), Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Laboratoire de Physique et Chimie Théoriques (LPCT), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), A.F.-M.is grateful to Generalitat Valenciana and the European Social Fund (project GV/2020/226) and the Ministerio de Ciencia e Innovación (projectCTQ2017-87054-C2-2-P and Juande la Cierva contract IJC2019-039297-I) for financial support., ANR-16-CE07-0013,PhotIron,Design de complexes de fer à propriétés photophysiques applicables(2016), ANR-10-IDEX-0002,UNISTRA,Par-delà les frontières, l'Université de Strasbourg(2010), ANR-20-SFRI-0012,STRAT'US,Façonner les talents en formation et en recherche à l'Université de Strasbourg(2020), ANR-17-EURE-0024,QMAT,Quantum Science and Nanomaterials(2017), European Project: Synergie LO0024898,FEDER,FIRELIGHT(2018), GROS, PHILIPPE C., Design de complexes de fer à propriétés photophysiques applicables - - PhotIron2016 - ANR-16-CE07-0013 - AAPG2016 - VALID, Initiative d'excellence - Par-delà les frontières, l'Université de Strasbourg - - UNISTRA2010 - ANR-10-IDEX-0002 - IDEX - VALID, Façonner les talents en formation et en recherche à l'Université de Strasbourg - - STRAT'US2020 - ANR-20-SFRI-0012 - SFRI - VALID, Quantum Science and Nanomaterials - - QMAT2017 - ANR-17-EURE-0024 - EURE - VALID, and FireLight : Photo-bio-active molecules and nanoparticles - FIRELIGHT - - FEDER2018-01-01 - 2022-12-31 - Synergie LO0024898 - VALID

Subjects
Computational chemistry, Denticity, 010405 organic chemistry, Chemistry, Iron, Bidentate ligands, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Excited state, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbene ligands, Ultrafast spectroscopy
Abstract

International audience; Iron complexes are promising candidates for the development of sustainable molecular photoactive materials as an alternative to those based on precious metals such as Ir, Pt or Ru. These compounds possess metal-ligand charge transfer (MLCT) transitions potentially of high interest for energy conversion or photocatalysis applications if the ultrafast deactivation via lower-lying metal-centred (MC) states can be impeded. Following an introduction describing the main design strategies used so far to increase the MLCT lifetimes, we review some of our latest contributions to the field regarding bidentate Fe(II) complexes comprising N-heterocyclic carbene ligands. The discussion covers all aspects from their synthesis to their characterization via photophysical, electrochemical and computational techniques. The impact of bidentate coordination together with the configuration (facial and meridional isomers) is analysed, finally highlighting the current challenges in this promising area.

Published
2021
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4. IrIII‐pyridoannelated N‐heterocyclic carbene complexes: potent theranostic agents via mitochondria targeting

Author

Anna Bonfiglio, Antoine Kichler, Conor McCartin, Philippe C. Gros, Chantal Daniel, Matteo Mauro, Sylvie Fournel, Ulises Carrillo, Cristina Cebrián, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Faculté de Pharmacie [Strasbourg], Université de Strasbourg (UNISTRA), Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Fondation pour la Recherche en Chimie, Idex Interdisciplinaire (CF/PN/CB/N°2017-973-5), ANR-10-LABX-0026,CSC,Center of Chemistry of Complex System(2010), ANR-10-IDEX-0002,UNISTRA,Par-delà les frontières, l'Université de Strasbourg(2010), ANR-18-CE06-0007,SOFTACTION,Actuateurs supramoléculaires sensibles à la lumière visible et proche infrarouge pour des applications biomédicales potentielles(2018), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), GROS, PHILIPPE C., Center of Chemistry of Complex System - - CSC2010 - ANR-10-LABX-0026 - LABX - VALID, Initiative d'excellence - Par-delà les frontières, l'Université de Strasbourg - - UNISTRA2010 - ANR-10-IDEX-0002 - IDEX - VALID, and APPEL À PROJETS GÉNÉRIQUE 2018 - Actuateurs supramoléculaires sensibles à la lumière visible et proche infrarouge pour des applications biomédicales potentielles - - SOFTACTION2018 - ANR-18-CE06-0007 - AAPG2018 - VALID

Subjects
010405 organic chemistry, Chemistry, chemistry.chemical_element, Mitochondrion, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Iridium, Phosphorescence, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021
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5. Vibrational Coherence Spectroscopy Identifies Ultrafast Branching in an Iron(II) Sensitizer

Author

Thomas J. Penfold, F. Hainer, A. Reddy Marri, Philippe C. Gros, Nicolò Alagna, Stefan Haacke, Tiago Buckup, Universität Heidelberg [Heidelberg], Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Newcastle University [Newcastle], Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), GROS, PHILIPPE C., Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010405 organic chemistry, Relaxation (NMR), Infrared spectroscopy, Charge (physics), 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Chemical physics, General Materials Science, Physical and Theoretical Chemistry, Spectroscopy, Ground state, Carbene, Excitation, Coherence (physics)
Abstract

International audience; The introduction of N-heterocyclic carbene ligands has greatly increased the lifetimes of metal-to-ligand charge transfer states (MLCT) in iron(II) complexes, making them promising candidates for photocatalytic applications. However, the spectrally elusive triplet metal-centered state (3MC) has been suggested to play a decisive role in the relaxation of the MLCT manifold to the ground state, shortening their lifetimes and consequently limiting the application potential. In this work, time-resolved vibrational spectroscopy and quantum chemical calculations are applied to shed light on the 3MCs’ involvement in the deactivation of the MLCT manifold of an iron(II) sensitizer. Two distinct symmetric Fe–L breathing vibrations at frequencies below 150 cm–1 are assigned to the 3MC and 3MLCT states by quantum chemical calculations. On the basis of this assignment, an ultrafast branching directly after excitation forms not only the long-lived 3MLCT but also the 3MC as an additional loss channel.

Published
2021
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6. Towards Iron(II) Complexes with Octahedral Geometry: Synthesis, Structure and Photophysical Properties

Author

Emmanuel Wenger, Philippe C. Gros, Stefan Haacke, Antonio Francés-Monerris, Antonio Monari, Bogdan A. Marekha, A. Doudouh, Mohamed Darari, Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique et Chimie Théoriques (LPCT), Universitat de València (UV), Max Planck Institute for Medical Research [Heidelberg], Max-Planck-Gesellschaft, Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and GROS, PHILIPPE C.

Subjects
[CHIM.INOR] Chemical Sciences/Inorganic chemistry, Ligand field theory, Coordination sphere, Materials science, Iron, Pharmaceutical Science, excited states dynamics, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Crystallography, X-Ray, Ligands, 010402 general chemistry, 01 natural sciences, Article, time-resolved spectroscopy, Analytical Chemistry, lcsh:QD241-441, Metal, X-Ray Diffraction, lcsh:Organic chemistry, Drug Discovery, Octahedral molecular geometry, [CHIM.CRIS]Chemical Sciences/Cristallography, iron (II) complexes, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Ferrous Compounds, [CHIM.CRIS] Chemical Sciences/Cristallography, Physical and Theoretical Chemistry, octahedral geometry, density functional theory, ComputingMilieux_MISCELLANEOUS, Molecular Structure, 010405 organic chemistry, Ligand, Organic Chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 0104 chemical sciences, 3. Good health, Crystallography, Octahedron, [CHIM.OTHE] Chemical Sciences/Other, Chemistry (miscellaneous), Excited state, visual_art, visual_art.visual_art_medium, Thermodynamics, Molecular Medicine, Density functional theory, [CHIM.OTHE]Chemical Sciences/Other
Abstract

The control of ligand-field splitting in iron (II) complexes is critical to slow down the metal-to-ligand charge transfer (MLCT)-excited states deactivation pathways. The gap between the metal-centered states is maximal when the coordination sphere of the complex approaches an ideal octahedral geometry. Two new iron(II) complexes (C1 and C2), prepared from pyridylNHC and pyridylquinoline type ligands, respectively, have a near-perfect octahedral coordination of the metal. The photophysics of the complexes have been further investigated by means of ultrafast spectroscopy and TD-DFT modeling. For C1, it is shown that&mdash, despite the geometrical improvement&mdash, the excited state deactivation is faster than for the parent pseudo-octahedral C0 complex. This unexpected result is due to the increased ligand flexibility in C1 that lowers the energetic barrier for the relaxation of 3MLCT into the 3MC state. For C2, the effect of the increased ligand field is not strong enough to close the prominent deactivation channel into the metal-centered quintet state, as for other Fe-polypyridine complexes.

Published
2020
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7. Photophysical Investigation of Iron(II) Complexes Bearing Bidentate Annulated Isomeric Pyridine-NHC Ligands

Author

Kevin Magra, Antonio Monari, Mohamed Darari, Antonio Francés-Monerris, Philippe C. Gros, Marc Beley, Cristina Cebrián, Edoardo Domenichini, Mariachiara Pastore, Xavier Assfeld, Stefan Haacke, Laboratoire de Physique et Chimie Théoriques (LPCT), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Universitat de València (UV), GROS, PHILIPPE C., Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Centre National de la Recherche Scientifique (CNRS)-Université de Lorraine (UL), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace, Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)

Subjects
[CHIM.INOR] Chemical Sciences/Inorganic chemistry, Denticity, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Chemical synthesis, chemistry.chemical_compound, Pyridine, Polymer chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, fused NHC, ComputingMilieux_MISCELLANEOUS, photophysics, Ligand, Minimum Energy Path, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, General Energy, iron complexes, chemistry, decay process, 0210 nano-technology, Luminescence, TD-DFT
Abstract

The possibility of achieving luminescent and photophysically active metal-organic compounds relies on the stabilization of charge transfer states and kinetically and thermodynamically blocking non-...

Published
2020
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8. Impact of the fac / mer Isomerism on the Excited-State Dynamics of Pyridyl-carbene Fe(II) Complexes

Author

Xavier Assfeld, Mohamed Darari, Antonio Francés-Monerris, Stefan Haacke, Cristina Cebrián, Edoardo Domenichini, Kevin Magra, Antonio Monari, Philippe C. Gros, Mariachiara Pastore, Marc Beley, GROS, PHILIPPE C., Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique et Chimie Théoriques (LPCT), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)

Subjects
[CHIM.INOR] Chemical Sciences/Inorganic chemistry, Denticity, Mechanism based, FOS: Physical sciences, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Physics - Chemical Physics, Ultrafast laser spectroscopy, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Chemical Physics (physics.chem-ph), 010405 organic chemistry, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Excited state, Ground state, Carbene
Abstract

The control of photophysical properties of iron complexes and especially of their excited states decay is a great challenge in the search for sustainable alternatives to noble metals in photochemical applications. Herein we report the synthesis and investigations of the photophysics of mer and fac iron complexes bearing bidentate pyridyl-NHC ligands, coordinating the iron with three ligand-field-enhancing carbene bonds. Ultrafast transient absorption spectroscopy reveals two distinct excited state populations for both mer and fac forms, ascribed to the populations of the T1 and the T2 states, respectively, which decay to the ground state via parallel pathways. We find 3-4 ps and 15-20 ps excited-state lifetimes, with respective amplitudes depending on the isomer. The longer lifetime exceeds the one reported for iron complexes with tridentate ligands analogues involving four iron-carbene bonds. By combining experimental and computational results, a mechanism based on the differential trapping of the triplet states in spin-crossover regions is proposed for the first time to explain the impact of the fac/ mer isomerism on the overall excited-state lifetimes. Our results clearly highlight the impact of bidentate pyridyl-NHC ligands on the photophysics of iron complexes, especially the paramount role of fac/ mer isomerism in modulating the overall decay process, which can be potentially exploited in the design of new Fe(II)-based photoactive compounds.

Published
2019
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9. Iron(II) complexes with diazinyl-NHC ligands: impact of π-deficiency of the azine core on photophysical properties

Author

Mohamed Darari, Cristina Cebrián, Edoardo Domenichini, Antonio Francés-Monerris, Kevin Magra, Xavier Assfeld, Stefan Haacke, Mariachiara Pastore, Antonio Monari, Philippe C. Gros, Marc Beley, Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique et Chimie Théoriques (LPCT), GROS, PHILIPPE C., Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)

Subjects
Ligand field theory, Pyrazine, 010405 organic chemistry, Ligand, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Azine, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Crystallography, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Spin crossover, Excited state, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Homoleptic, Carbene
Abstract

International audience; Ligand field enhancing N-heterocyclic carbene (NHC) ligands were recently shown to prevent photo-induced spin crossover in Fe(II) complexes due to their intricate effects on the electronic excited state structure. Due to their pico- to nanosecond lifetimes, these complexes are now good candidates for photo-sensitizing applications. Herein we report the synthesis and photophysical characterization of a new family of homoleptic Fe(II) complexes with C^N^C ligands involving diazines as the central N-heteroaromatic ligand. For these four carbene bond complexes, ultrafast transient absorption spectroscopy revealed a significant improvement of the excited-state lifetime. A record 32 ps lifetime was measured for a complex bearing a ligand combining a π-deficient pyrazine nucleus and a benzimidazolylidene as NHC. When compared to other azine-based ligands investigated, we argue that the lifetimes are modulated by a small excited state barrier expressing the ability of the ligand to reach the Fe–N distance needed for internal conversion to the ground state

Published
2019
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10. Design of New Iron-based Sensitizers for Light harvesting and Electron-transfer

Author

Gros, Philippe, Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and GROS, PHILIPPE C.

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2018

11. Synthesis and Computational Study of a Pyridylcarbene Fe(II) Complex: Unexpected Effects of fac / mer Isomerism in Metal-to-Ligand Triplet Potential Energy Surfaces

Author

Cristina Cebrián, Edoardo Domenichini, Xavier Assfeld, Philippe C. Gros, Antonio Francés-Monerris, Antonio Monari, Kevin Magra, Mohamed Darari, Stefan Haacke, Mariachiara Pastore, Marc Beley, GROS, PHILIPPE C., Design de complexes de fer à propriétés photophysiques applicables - - PhotIron2016 - ANR-16-CE07-0013 - AAPG2016 - VALID, Laboratoire de Physique et Chimie Théoriques (LPCT), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), ANR-16-CE07-0013,PhotIron,Design de complexes de fer à propriétés photophysiques applicables(2016), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)

Subjects
Absorption spectroscopy, Population, Zonal and meridional, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Metal, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Singlet state, Physical and Theoretical Chemistry, education, ComputingMilieux_MISCELLANEOUS, education.field_of_study, Ligand, Chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 021001 nanoscience & nanotechnology, Potential energy, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, visual_art, Potential energy surface, visual_art.visual_art_medium, 0210 nano-technology
Abstract

The synthesis and the steady-state absorption spectrum of a new pyridine-imidazolylidene Fe(II) complex (Fe-NHC) are presented. A detailed mechanism of the triplet metal-to-ligand charge-transfer states decay is provided on the basis of minimum energy path (MEP) calculations used to connect the lowest-lying singlet, triplet, and quintet state minima. The competition between the different decay pathways involved in the photoresponse is assessed by analyzing the shapes of the obtained potential energy surfaces. A qualitative difference between facial (fac) and meridional (mer) isomers’ potential energy surface (PES) topologies is evidenced for the first time in iron-based complexes. Indeed, the mer complex shows a steeper triplet path toward the corresponding 3MC minimum, which lies at a lower energy as compared to the fac isomer, thus pointing to a faster triplet decay of the former. Furthermore, while a major role of the metal-centered quintet state population from the triplet 3MC region is excluded, we i...

Published
2018
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12. From Ruthenium to Iron Sensitizers: A Challenge towards more Ecofriendly Hybrid Solar Cells

Author

Gros, Philippe, Structure et Réactivité des Systèmes Moléculaires Complexes (SRSMC), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and GROS, PHILIPPE C.

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017

13. From Ruthenium to Iron Sensitizers: The Challenging Chemical Tuning of Photophysical Properties

Author

Gros, Philippe, GROS, PHILIPPE C., Structure et Réactivité des Systèmes Moléculaires Complexes (SRSMC), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017

14. Interfacial charge separation and photovoltaic efficiency in Fe(ii)–carbene sensitized solar cells

Author

Xavier Assfeld, Mariachiara Pastore, Antonio Monari, Thibaut Duchanois, Stefan Haacke, Philippe C. Gros, Li Liu, Structure et Réactivité des Systèmes Moléculaires Complexes ( SRSMC ), Université de Lorraine ( UL ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Physique et Chimie des Matériaux de Strasbourg ( IPCMS ), Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ) -Matériaux et nanosciences d'Alsace, Université de Strasbourg ( UNISTRA ) -Université de Haute-Alsace (UHA) Mulhouse - Colmar ( Université de Haute-Alsace (UHA) ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Strasbourg ( UNISTRA ) -Université de Haute-Alsace (UHA) Mulhouse - Colmar ( Université de Haute-Alsace (UHA) ) -Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Centre National de la Recherche Scientifique ( CNRS ) -Réseau nanophotonique et optique, Université de Strasbourg ( UNISTRA ) -Université de Haute-Alsace (UHA) Mulhouse - Colmar ( Université de Haute-Alsace (UHA) ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Strasbourg ( UNISTRA ), ANR-10-IDEX-0002-02/11-LABX-0058,NIE,Nanostructures en Interaction avec leur Environnement ( 2010 ), Structure et Réactivité des Systèmes Moléculaires Complexes (SRSMC), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), ANR-16-CE07-0013,PhotIron,Design de complexes de fer à propriétés photophysiques applicables(2016), ANR-10-IDEX-0002,UNISTRA,Par-delà les frontières, l'Université de Strasbourg(2010), GROS, PHILIPPE C., Design de complexes de fer à propriétés photophysiques applicables - - PhotIron2016 - ANR-16-CE07-0013 - AAPG2016 - VALID, Initiative d'excellence - Par-delà les frontières, l'Université de Strasbourg - - UNISTRA2010 - ANR-10-IDEX-0002 - IDEX - VALID, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ab initio, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, Photochemistry, Iron(II) complexes, 01 natural sciences, 7. Clean energy, DFT, Molecular engineering, chemistry.chemical_compound, Deprotonation, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Electronic effect, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carboxylate, Physical and Theoretical Chemistry, Homoleptic, electron recombination, ComputingMilieux_MISCELLANEOUS, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 021001 nanoscience & nanotechnology, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 0104 chemical sciences, dye-sensitized TiO2, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dye-sensitized solar cell, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, chemistry, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, electron injection, 0210 nano-technology, Carbene
Abstract

International audience; The first combined theoretical and photovoltaic characterization of both homoleptic and heteroleptic Fe(II)–carbene sensitized photoanodes in working dye sensitized solar cells (DSSCs) has been performed. Three new heteroleptic Fe(II)–NHC dye sensitizers have been synthesized, characterized and tested. Despite an improved interfacial charge separation in comparison to the homoleptic compounds, the heteroleptic complexes did not show boosted photovoltaic performances. The ab initio quantitative analysis of the interfacial electron and hole transfers and the measured photovoltaic data clearly evidenced fast recombination reactions for heteroleptics, even associated with un unfavorable directional electron flow, and hence slower injection rates, in the case of homoleptics. Notably, quantum mechanics calculations revealed that deprotonation of the not anchored carboxylic function in the homoleptic complex can effectively accelerate the electron injection rate and completely suppress the electron recombination to the oxidized dye. This result suggests that introduction of strong electron-donating substituents on the not-anchored carbene ligand in heteroleptic complexes, in such a way of mimicking the electronic effects of the carboxylate functionality, should yield markedly improved interfacial charge generation properties. The present results, providing for the first time a detailed understanding of the interfacial electron transfers and photovoltaic characterization in Fe(II)–carbene sensitized solar cells, open the way to a rational molecular engineering of efficient iron-based dyes for photoelectrochemical applications.

Published
2016
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