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19 results on '"Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR)"'

1. A Porphyrin Dimer–GdDOTA Conjugate as a Theranostic Agent for One- and Two-Photon Photodynamic Therapy and MRI

Author

Sébastien Jenni, Barbara Ventura, Célia S. Bonnet, Éva Tóth, Angélique Sour, Frédéric Bolze, Valérie Heitz, Agnès Pallier, Julie Schmitt, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Conception et application de molécules bioactives (CAMB), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Université de Strasbourg (UNISTRA), ISOF-CNR, Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), 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), and LEGOUPIL, Laëtitia

Subjects
Porphyrins, [SDV]Life Sciences [q-bio], medicine.medical_treatment, MRI contrast agent, Dimer, Biomedical Engineering, Pharmaceutical Science, Bioengineering, Photodynamic therapy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Theranostic Nanomedicine, HeLa, chemistry.chemical_compound, Nuclear magnetic resonance, Two-photon excitation microscopy, Heterocyclic Compounds, Theranostic agent, Neoplasms, Organometallic Compounds, medicine, Humans, [CHIM.COOR]Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS, Pharmacology, Photons, Photosensitizing Agents, Singlet Oxygen, biology, Singlet oxygen, Organic Chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, Magnetic Resonance Imaging, Porphyrin, 0104 chemical sciences, 3. Good health, [SDV] Life Sciences [q-bio], Photochemotherapy, chemistry, Porphyrin dimer, 0210 nano-technology, Dimerization, MRI, HeLa Cells, Biotechnology, Conjugate
Abstract

International audience; A molecular theranostic agent designed for photodynamic therapy (PDT) treatment in the near-infrared and for imaging tissue tumors with magnetic resonance imaging (MRI) is reported. It consists of a linear pi-conjugated Zn(II) porphyrin dimer linked at each extremity to a GdDOTA-type complex. This agent has shown very promising potential for PDT applications with good singlet oxygen generation in DMSO and high linear absorption in the near- infrared (lambda(max) = 746 nm, epsilon approximate to 10(5) M-1 cm(-1)). Moreover, this molecule has a propensity for two-photon excited PDT with high two-photon cross sections (similar to 8000 GM in 880-930 nm range), which should allow for deeper tumor treatments and higher spatial precision as compared to conventional one-photon PDT. Regarding the MRI contrast agent properties, the molecule has shown superior relaxivity (14.4 mM(-1) s(-1) at 40 MHz, 298 K) in comparison to clinical contrast agents and the ability to be internalized in cells, thanks to its amphiphilic character. Irradiation of HeLa cells using either one-photon (740 nm) or two-photon excitation (910 nm) has led in both cases to important cell death.

Published
2018
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2. Multiscale time-resolved fluorescence study of a glycogen phosphorylase inhibitor combined with quantum chemistry calculations

Author

Dimitra Markovitsi, Konstantinos F. Mavreas, Michael Mamais, Thanasis Gimisis, Filippo Monti, Evangelia D. Chrysina, Alessandro Venturini, Thomas Gustavsson, Valentin Maffeis, Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), National and Kapodistrian University of Athens (NKUA), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Dynamique et Interactions en phase Condensée (DICO), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Hellenic Research Foundation [Athens], Istituto CNR per la Sintesi Organica e Fotoreattivita (ISOF), European Project: 284464,EC:FP7:INFRA,FP7-INFRASTRUCTURES-2011-1,LASERLAB-EUROPE(2012), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Consiglio Nazionale delle Ricerche (CNR), Biomolécules Excitées (DICO), and Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inhibitor, Population, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, DFT, Benzoates, Fluorescence spectroscopy, Glycogen phosphorylase, chemistry.chemical_compound, Computational chemistry, Physical and Theoretical Chemistry, Enzyme Inhibitors, education, Conformational isomerism, education.field_of_study, Chemistry, Glycogen Phosphorylase, 021001 nanoscience & nanotechnology, Fluorescence, Multiscale fluorescence, 3. Good health, 0104 chemical sciences, Acridone, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Spectrometry, Fluorescence, Excited state, Quantum Theory, Thermodynamics, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Time-resolved spectroscopy, 0210 nano-technology, Acridones
Abstract

International audience; A fluorescence study of N1-(β-D-glucopyranosyl)-N4-[2-acridin-9(10H)-onyl]-cytosine (GLAC), the first fluorescent potent inhibitor of glycogen phosphorylase (GP), in neutral aqueous solution, is presented herein. Quantum chemistry (TD-DFT) calculations show the existence of several conformers both in the ground and first excited states. They result from rotations of the acridone and cytosine moieties around an NH bridge which may lead to the formation of non-emitting charge-transfer states. The fingerprints of various conformers have been detected by time-resolved fluorescence spectroscopy (fluorescence upconversion and time-correlated single photon counting) and identified using as criteria their energy, polarization and relative population resulting from computations. Such an analysis should contribute to the design of new GP inhibitors with better fluorescence properties, suitable for imaging applications.

Published
2019
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3. Dinuclear Copper(I) Complexes Combining Bis(diphenylphosphanyl)acetylene with 1,10-Phenanthroline Ligands

Author

Michel Holler, Enrico Leoni, Filippo Monti, Alix Sournia-Saquet, Nicola Armaroli, Béatrice Delavaux-Nicot, Jean-François Nierengarten, Iwona Nierengarten, Laboratoire de chimie moléculaire (LCM), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratorio Tecnologie dei Materiali Faenza, ENEA, Agenzia Nazionale per le nuove Tecnologie, l’energia e lo sviluppo economico sostenibile (ENEA), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Agenzia Nazionale per le nuove Tecnologie, l’energia e lo sviluppo economico sostenibile = Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), International Center for Frontier Research in Chemistry, LabEx 'Chimie des Systèmes Complexes', CNR (PHEEL), Nierengarten, J. -F., Nierengarten, I., Holler, M., Sournia-Saquet, A., Delavaux-Nicot, B., Leoni, E., Monti, F., and Armaroli, N.

Subjects
Luminescence, Dinuclear complexes, Phenanthroline, Substituent, chemistry.chemical_element, Phosphanes, 02 engineering and technology, Crystal structure, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Neocuproine, 03 medical and health sciences, chemistry.chemical_compound, 0302 clinical medicine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Homoleptic, Copper, 030304 developmental biology, 0303 health sciences, Ligand, Metallacycle, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, Dinuclear complexe, Crystallography, chemistry, 030220 oncology & carcinogenesis, 0210 nano-technology
Abstract

Dinuclear copper(I) complexes have been prepared starting from bis(diphenylphosphanyl)acetylene (dppa), [Cu(CH3CN)(4)](BF4) and various 1,10-phenanthroline ligands (NN), namely 1,10-phenanthroline (phen), neocuproine (dmp), bathophenanthroline (Bphen), bathocuproine (Bdmp) and 2-phenyl-1,10-phenanthroline (mpp). The resulting [Cu-2(mu-dppa)(2)(NN)(2)](BF4)(2) complexes have been thus obtained in excellent yields (88 to 94 %). X-ray crystal structure analysis of four complexes revealed that the 10-membered dimetallacycle adopts a chair-like conformation in the solid state. Detailed variable temperature NMR investigations have evidenced dynamic coordination/decoordination of the NN ligands as well as ligand exchange reactions. At high temperature (100 degrees C), entropic effects tend to destabilize the dinuclear heteroleptic complexes. As a result, homoleptic mononuclear complexes, i.e. [Cu(NN)(2)](+) and undefined dppa copper(I) complexes, start to appear in solution. In contrast, the heteroleptic coordination scenario is almost exclusively favored at lower temperatures. For most of the dinuclear complexes, the 10-membered dimetallacycle remains flexible and chair-to-chair interconversion occurs faster than the NMR timescale even at -70 degrees C. In the particular case of the mpp derivative, the bulky phenyl substituent prevents the isomerization of the metallacycle and thus contributes to rigidify the structure. This rigidification has a dramatic effect on the emission properties of this particular compound. The emission quantum yield of [Cu-2(mu-dppa)(2)(mpp)(2)](BF4)(2) is effectively one order of magnitude higher when compared to all the other complexes in this series (20 % vs. 0.3-1.7 % in the solid state).

Published
2019
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4. Cyclometalated N-heterocyclic carbene iridium( iii ) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds

Author

Hani Amouri, Geoffrey Gontard, Antoine Groué, Pierre-Henri Lanoë, Filippo Monti, Marie-Noëlle Rager, Nicola Armaroli, Andrea Barbieri, Jonny Chan, Anny Jutand, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service de Résonance Magnétique Nucléaire, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Gulliver (UMR 7083), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), IRPPS-CNR, Salerno, and Università degli Studi di Salerno (UNISA)

Subjects
Iridium complexes, Denticity, Phosphorescence, 010405 organic chemistry, Ligand, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, Chromophore, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Polymer chemistry, Imidazole, Moiety, Iridium, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract

A series of cyclometalated N-heterocyclic carbene complexes of the general formula [Ir(CN)(2)(CC:)] has been prepared. Two sets of compounds were designed, those where (CC:) represents a bidentate naphthalimide-substituted imidazolylidene ligand and (CN) = ppy (3a), F2ppy (4a), bzq (5a) and those where (CC:) represents a naphthalimide-substituted benzimidazolylidene ligand and (CN) = ppy (3b), F2ppy (4b), bzq (5b). The naphthalimide-imidazole and naphthalimide-benzimidazole ligands 1a,b and the related imidazolium and benzimidazolium salts 2a, b were also prepared and fully characterized. The N-heterocyclic carbene Ir(III) complexes have been characterized by NMR spectroscopy, cyclic voltammetry and elemental analysis. Moreover, the molecular structures of one imidazolium salt and four Ir(III) complexes were determined by single-crystal X-ray diffraction. The structures provide us with valuable information, most notably the orientation of the naphthalimide chromophore with respect to the N-heterocyclic carbene moiety. All compounds are luminescent at room temperature and in a frozen solvent at 77 K, exhibiting a broad emission band that extends beyond 700 nm. The presence of the naphthalimide moiety changes the character of the lowest excited state from (MLCT)-M-3 to (LC)-L-3, as corroborated by DFT and TD-DFT calculations. Remarkably, replacing imidazole with a benzimidazole unit improves the quantum yields of these compounds by decreasing the k(nr) values which is an important feature for optimized emission performance. These studies provide valuable insights about a novel class of N-heterocyclic carbene-based luminescent complexes containing organic chromophores and affording metal complexes emitting across the red-NIR range.

Published
2018
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5. Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands: Rationalization of the Photophysical and Electrochemical Properties

Author

John Mohanraj, Meera Mohankumar, Iwona Nierengarten, Michel Holler, Béatrice Delavaux-Nicot, Alix Sournia-Saquet, Jean-François Nierengarten, Nicola Armaroli, Filippo Monti, Enrico Leoni, Leoni, E., Mohanraj, J., Holler, M., Mohankumar, M., Nierengarten, I., Monti, F., Sournia-Saquet, A., Delavaux-Nicot, B., Jean-Francois, Nierengarten, Armaroli, N., Leoni, Enrico, Mohanraj, John, Holler, Michel, Mohankumar, Meera, Nierengarten, Iwona, Monti, Filippo, Sournia-Saquet, Alix, Delavaux-Nicot, Béatrice, Jean-Francois Nierengarten, null, Armaroli, Nicola, Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Laboratoire de chimie moléculaire (LCM), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Cu(I) complexes, Luminescence, Absorption spectroscopy, 010405 organic chemistry, Phenanthroline, Excited states, chemistry.chemical_element, Ether, Crystal structure, 010402 general chemistry, Electrochemistry, 01 natural sciences, Medicinal chemistry, Copper, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Density functional theory, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Phosphine
Abstract

The electronic and structural properties of ten heteroleptic [Cu(NN)(PP)]+ complexes have been investigated. NN indicates 1,10-phenanthroline (phen) or 4,7-diphenyl-1,10-phenanthroline (Bphen); each of these ligands is combined with five PP bis-phosphine chelators, i.e., bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), and bis[(2-diphenylphosphino)phenyl] ether (POP). All complexes are mononuclear, apart from those based on dppm, which are dinuclear. Experimental data - also taken from the literature and including electrochemical properties, X-ray crystal structures, UV-vis absorption spectra in CH2Cl2, luminescence spectra and lifetimes in solution, in PMMA, and as powders - have been rationalized with the support of density functional theory calculations. Temperature dependent studies (78-358 K) have been performed for selected complexes to assess thermally activated delayed fluorescence. The main findings are (i) dependence of the ground-state geometry on the crystallization conditions, with the same complex often yielding different crystal structures; (ii) simple model compounds with imposed C2v symmetry ([Cu(phen)(PX3)2]+ X = H or CH3) are capable of modeling structural parameters as a function of the P-Cu-P bite angle, which plays a key role in dictating the overall structure of [Cu(NN)(PP)]+ complexes; (iii) as the P-Cu-P angle increases, the energy of the metal-to-ligand charge transfer absorption bands linearly increases; (iv) the former correlation does not hold for emission spectra, which are red-shifted for the weaker luminophores; (v) the larger the number of intramolecular π-interactions within the complex in the ground state, the higher the luminescence quantum yield, underpinning a geometry locking effect that limits the structural flattening of the excited state. This work provides a general framework to rationalize the structure-property relationships of [Cu(NN)(PP)]+, a class of compounds of increasing relevance for electroluminescent devices, photoredox catalysis, and solar-to-fuels conversion, which so far have been investigated in an unsystematic fashion, eluding a comprehensive understanding. © Copyright 2018 American Chemical Society.

Published
2018
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6. Heteroleptic copper(I) pseudorotaxanes incorporating macrocyclic phenanthroline ligands of different sizes

Author

Nicola Armaroli, Joanna M. Malicka, Meera Mohankumar, Jean-Pierre Sauvage, Michel Holler, Béatrice Delavaux-Nicot, Elisa Bandini, Eric Meichsner, Massimo Cocchi, Jean-François Nierengarten, Enrico Leoni, Filippo Monti, Frédéric Niess, Laboratoire de chimie moléculaire (LCM), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Science et d'ingénierie supramoléculaires (ISIS), 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 Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-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)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Laboratorio Tecnologie dei Materiali Faenza, ENEA, Agenzia Nazionale per le nuove Tecnologie, l’energia e lo sviluppo economico sostenibile (ENEA), Laboratory for Micro and Submicro Enabling Technologies of the Emilia-Romagna Region (MIST E-R), Università degli Studi di Ferrara (UniFE), Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche [Roma] (CNR), Mohankumar, Meera, Holler, Michel, Meichsner, Eric, Nierengarten, Jean-François, Niess, Frédéric, Sauvage, Jean-Pierre, Delavaux-Nicot, Béatrice, Leoni, Enrico, Monti, Filippo, Malicka, Joanna M., Cocchi, Massimo, Bandini, Elisa, Armaroli, Nicola, Mohankumar, M., Holler, M., Meichsner, E., Nierengarten, J. -F., Niess, F., Sauvage, J. -P., Delavaux-Nicot, B., Leoni, E., Monti, F., Malicka, J. M., Cocchi, M., Bandini, E., and Armaroli, N.

Subjects
Photoluminescence, oled, Rotaxanes, Phenanthroline, chemistry.chemical_element, Ether, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Catalysi, chemistry.chemical_compound, Colloid and Surface Chemistry, luminescence, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Methyl methacrylate, Cu(I) complexes, 010405 organic chemistry, Chemistry (all), General Chemistry, Copper, 0104 chemical sciences, 3. Good health, Crystallography, chemistry, Macrocyclic ligand, Absorption (chemistry), Luminescence
Abstract

International audience; A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)]+ (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20–30%. The smallest system [Cu(m30)(POP)]+ shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (∼40−45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78–338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet–triplet energy gap compared to the reference compound [Cu(dmp)(POP)]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)]+) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)]+, which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.

Published
2018
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7. Efficient Photoinduced Energy and Electron Transfer in Zn II -Porphyrin/Fullerene Dyads with Interchromophoric Distances up to 2.6 nm and No Wire-like Connectivity

Author

John Mohanraj, Nicola Armaroli, Jean-François Nierengarten, Uwe Hahn, Béatrice Delavaux-Nicot, Julien Iehl, Maida Vartanian, Fernando Langa, María Vizuete, Andrea Barbieri, Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), IRPPS-CNR, Salerno, Università degli Studi di Salerno (UNISA), Instituto de Nanociencia, Nanotecnología y Materiales Moleculares (INAMOL), Universidad de Castilla-La Mancha (UCLM), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des Matériaux Moléculaires, Laboratoire d'innovation moléculaire et applications (LIMA), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), and Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS)

Subjects
Fullerene, Luminescence, Quantum yield, Porphyrinoids, Conjugated system, 010402 general chemistry, Photochemistry, 01 natural sciences, 7. Clean energy, Catalysis, Photoinduced electron transfer, Electron transfer, chemistry.chemical_compound, [CHIM]Chemical Sciences, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Chromophore, Porphyrin, 0104 chemical sciences, Benzonitrile, chemistry, Energy transfer, Fullerenes
Abstract

International audience; The dyads 1–3 made of an alkynylated ZnII–porphyrin and a bis‐methanofullerene derivative connected through a copper‐catalyzed azide–alkyne cycloaddition have been synthesized. The porphyrin and fullerene chromophores are separated through a bridge made of a bismethanofullerene tether linked to different spacers conjugated to the porphyrin moiety [i.e., m‐phenylene (1), p‐phenylene (2), di‐p‐phenylene‐ethynylene (3)]. Compounds 1–3 exhibit relatively rigid structures with an interchromophoric separation of 1.7, 2.0, and 2.6 nm, respectively, and no face‐to‐face or direct through‐bond conjugation. The photophysical properties of compounds 1–3 have been investigated in toluene and benzonitrile with steady‐state and time‐resolved techniques as well as model calculations on the Förster energy transfer. Excited‐state interchromophoric electronic interactions are observed with a distinct solvent and distance dependence. The latter effect is evidenced in benzonitrile, where compounds 1 and 2 exhibit a photoinduced electron transfer in the Marcus‐inverted region, with charge‐separated (CS) states living for 0.44 and 0.59 μs, respectively, whereas compound 3 only undergoes energy transfer, as in apolar toluene. The quantum yield of the charge separation (φCS) of compounds 1 and 2 in benzonitrile is ≥0.75. It is therefore demonstrated that photoinduced energy and electron transfers in porphyrin–fullerene systems with long interchromophoric distances may efficiently occur also when the bridge does not provide a wire‐like conjugation and proceed through the triplet states of the chromophoric moieties.

Published
2017
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8. A New Potent Inhibitor of Glycogen Phosphorylase Reveals the Basicity of the Catalytic Site

Author

Filippo Monti, Dimitra Markovitsi, Alessandra Degli Esposti, Evangelia D. Chrysina, Alessandro Venturini, Virginia Kouloumoundra, Thomas Gustavsson, Thanasis Gimisis, Michael Mamais, National and Kapodistrian University of Athens (NKUA), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Biomolécules Excitées (DICO), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Gulliver (UMR 7083), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Hellenic Research Foundation [Athens], National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Dynamique et Interactions en phase Condensée (DICO), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)

Subjects
0301 basic medicine, Absorption spectroscopy, Stereochemistry, Static Electricity, 010402 general chemistry, Crystallography, X-Ray, 01 natural sciences, Catalysis, 03 medical and health sciences, Glycogen phosphorylase, chemistry.chemical_compound, Catalytic Domain, Fluorescent protein, Enzyme Inhibitors, Potent Inhibitor, chemistry.chemical_classification, Binding Sites, GLAC, Organic Chemistry, Glycogen Phosphorylase, Hydrogen Bonding, General Chemistry, Optical spectra, 0104 chemical sciences, 3. Good health, Acridone, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, 030104 developmental biology, Enzyme, Glucose, chemistry, ddc:540, Quantum Theory, acridone derivative, Derivative (chemistry), Acridones
Abstract

International audience; The design and synthesis of a glucose-based acridone derivative (GLAC), a potent inhibitor of glycogen phosphorylase (GP) are described. GLAC is the first inhibitor of glycogen phosphorylase, the electronic absorption properties of which are clearly distinguishable from those of the enzyme. This allows probing subtle interactions in the catalytic site. The GLAC absorption spectra, associated with X-ray crystallography and quantum chemistry calculations, reveal that part of the catalytic site of GP behaves as a highly basic environment in which GLAC exists as a bis-anion. This is explained by water-bridged hydrogen-bonding interactions with specific catalytic site residues.

Published
2017
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9. Luminescent Cyclometalated Platinum Complexes with π-Bonded Catecholate Organometallic Ligands

Author

Hani Amouri, Elisa Bandini, Alessandra Degli Esposti, Jamal Moussa, Aruny Loch, Lise-Marie Chamoreau, Andrea Barbieri, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)

Subjects
010405 organic chemistry, Chemistry, Solid-state, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Supramolecular assembly, Inorganic Chemistry, Crystallography, [CHIM]Chemical Sciences, Density functional theory, Catecholate Organometallic Ligands, Physical and Theoretical Chemistry, Platinum, Luminescence, Cyclometalated Platinum Complexes
Abstract

A series of cyclometalated platinum(II) complexes of the type [(ppy)Pt(LM)]n+ (n = 0, 1) with ?-bonded catecholates acting as organometallic ligands (LM) have been prepared and characterized by analytical techniques. In addition, the structures of two complexes of the series were determined by single-crystal X-ray diffraction. The packing shows the formation of a 1D supramolecular assembly generated by dPt-?Cp* interactions among individual units. All complexes are luminescent in the solid state and in solution media. The results of photophysics have been rationalized by means of density functional theory (DFT) and time-dependent DFT investigations.A series of cyclometalated platinum(II) complexes of the type [(ppy)Pt(LM)]n+ (n = 0, 1) with ?-bonded catecholates acting as organometallic ligands (LM) have been prepared and characterized by analytical techniques. In addition, the structures of two complexes of the series were determined by single-crystal X-ray diffraction. The packing shows the formation of a 1D supramolecular assembly generated by dPt-?Cp* interactions among individual units. All complexes are luminescent in the solid state and in solution media. The results of photophysics have been rationalized by means of density functional theory (DFT) and time-dependent DFT investigations.

Published
2017
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10. Four Gadolinium(III) Complexes Appended to a Porphyrin: A Water-Soluble Molecular Theranostic Agent with Remarkable Relaxivity Suited for MRI Tracking of the Photosensitizer

Author

Célia S. Bonnet, Barbara Ventura, Paulo Loureiro de Sousa, Angélique Sour, Valérie Heitz, Ana Ortí-Suárez, Sébastien Jenni, Éva Tóth, Chrystelle Po, Agnès Pallier, Julie Schmitt, Frédéric Bolze, Université de Strasbourg (UNISTRA), Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-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 Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-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), Conception et application de molécules bioactives (CAMB), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique Biologique, Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-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
Porphyrins, Light, MRI contrast agent, medicine.medical_treatment, Gadolinium, Proton Magnetic Resonance Spectroscopy, [SDV]Life Sciences [q-bio], chemistry.chemical_element, Photodynamic therapy, 010402 general chemistry, 01 natural sciences, Theranostic Nanomedicine, Inorganic Chemistry, chemistry.chemical_compound, Nuclear magnetic resonance, Coordination Complexes, medicine, Humans, Photosensitizer, Yttrium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Photosensitizing Agents, Cell Death, 010405 organic chemistry, Singlet oxygen, HIGH MAGNETIC-FIELD, CONTRAST AGENTS, PHOTODYNAMIC THERAPY, CANCER-THERAPY, DRUG-DELIVERY, BRAIN-TUMORS, NANOPARTICLES, RESONANCE, NANOMEDICINE, DESIGN, Water, Porphyrin, Magnetic Resonance Imaging, 0104 chemical sciences, chemistry, Solubility, Chimie/Chimie inorganique, Phototoxicity, Lysosomes, Conjugate, HeLa Cells
Abstract

A molecular theranostic agent for magnetic resonance imaging (MRI) and photodynamic therapy (PDT) consisting of four [GdDTTA](-) complexes (DTTA(4-) = diethylenetriamine-N,N,N",N"-tetraacetate) linked to a meso-tetraphenylporphyrin core, as well as its yttrium(III) analogue, was synthesized. A variety of physicochemical methods were used to characterize the gadolinium(III) conjugate 1 both as an MRI contrast agent and as a photosensitizer. The proton relaxivity measured in H2O at 20 MHz and 25 degrees C, r(1) = 43.7 mmol(-1) s(-1) per gadolinium center, is the highest reported for a bishydrated gadolinium(III)-based contrast agent of medium size and can be related to the rigidity of the molecule. The complex displays also a remarkable singlet oxygen quantum yield of phi(Delta) = 0.45 in H2O, similar to that of a meso-tetrasulfonated porphyrin. We also evidenced the ability of the gadolinium(III) conjugate to penetrate in cancer cells with low cytotoxicity. Its phototoxicity on Hela cells was evaluated following incubation at low micromolar concentration and moderate light irradiation (21 J cm(-2)) induced 50% of cell death. Altogether, these results demonstrate the high potential of this conjugate as a theranostic agent for MRI and PDT.

Published
2016
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11. Deep-Red Phosphorescent Iridium(III) Complexes with Chromophoric N-Heterocyclic Carbene Ligands: Design, Photophysical Properties, and DFT Calculations

Author

Nicola Armaroli, Pierre-Henri Lanoë, Geoffrey Gontard, Hani Amouri, Jonny Chan, Andrea Barbieri, Filippo Monti, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Gulliver (UMR 7083), Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), IRPPS-CNR, Salerno, Università degli Studi di Salerno = University of Salerno (UNISA), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Consiglio Nazionale delle Ricerche (CNR), and Università degli Studi di Salerno (UNISA)

Subjects
Luminescence, 010405 organic chemistry, Ligand, chemistry.chemical_element, Chromophore, Iridium, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Charge transfer, Photophysics, chemistry, Excited state, Moiety, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Phosphorescence, Carbene ligands, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract

The synthesis of three deep-red-emitting iridium(III) complexes featuring a naphthalimide N-heterocyclic carbene ligand was investigated. The introduction of this organic chromophore onto the carbene moiety changed the character of the lowest excited state from triplet metal-to-ligand charge transfer to triplet ligand centered, as corroborated by time-dependent DFT calculations. All complexes displayed a naphthalimide- based deep-red phosphorescence emission above lambda = 630 nm in polymer matrix with good quantum yields (Phi approximate to 0.2) and long lifetimes.

Published
2016
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12. Deep-Red Phosphorescent Iridium(III) Complexes with Chromophoric N-Heterocyclic Carbene Ligands: Design, Photophysical Properties, and DFT Calculations (Eur. J. Inorg. Chem. 11/2016)

Author

Pierre-Henri Lanoë, Geoffrey Gontard, Filippo Monti, Andrea Barbieri, Jonny Chan, Hani Amouri, Nicola Armaroli, Architectures Moléculaires (A.R.C), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Consiglio Nazionale delle Ricerche (CNR)

Subjects
010405 organic chemistry, Chemistry, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM]Chemical Sciences, Iridium, Phosphorescence, Luminescence, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; no abstract

Published
2016
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13. Synthesis and Photophysical Properties of Copper(I) Complexes Obtained from 1,10‐Phenanthroline Ligands with Increasingly Bulky 2,9‐Substituents

Author

Alix Saquet, Carine Duhayon, Michel Holler, Omar Moudam, Nicola Armaroli, Gianluca Accorsi, Richard Welter, Béatrice Delavaux-Nicot, Jean-François Nierengarten, Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Louis Pasteur - Laboratoire Decomet (UMR 7177-LC3), Université Louis Pasteur - Strasbourg I-Commencez à saisir le nom d'une tutelle, and Ecole nationale supérieure de chimie, polymères et materiaux de strasbourg (ECPM)

Subjects
Electronic structure, Luminescence, Absorption spectroscopy, Phenanthroline, chemistry.chemical_element, 010402 general chemistry, Electrochemistry, Photochemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Quenching (fluorescence), 010405 organic chemistry, Copper, 0104 chemical sciences, 3. Good health, Crystallography, chemistry, Ground state
Abstract

In this paper, we describe the synthesis and the electronic properties of a series of [Cu(NN) 2 ] + systems. The NN ligands investigated are 2,9-bis[(tert-butyldimethylsilyloxy)methyl]-1,10-phenanthroline (1), 2,9-bis[(triisopropylsilyloxy)methyl]-1,10-phenanthroline (2), 2,9-bis[(tert-butyldiphenylsilyl-moxy)ethyl]-1,10-phenanthroline (3), 2,9-bis[2,6-bis(benzyl-oxy)phenethyl]-1,10-phenanthroline (4) and 2-(1,3-diphenylpropan-2-yl)-9-phenethyl-1,10-phenanthroline (5). The electrochemical properties and the ground state electronic absorption spectra of Cu(1) 2 ―Cu(5) 2 are in line with the classical behaviour of such [Cu(NN) 2 ] + derivatives. Whereas all the compounds exhibit MLCT luminescence centered around 630―650 nm, the emission quantum yields and the lifetimes are dramatically different as a function of stereo-electronic effects and/or the possibility of internal exciplex quenching when oxygen-containing functional groups are attached to the phenanthroline ligands.

Published
2009
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14. Unravelling molecular mechanisms in the fluorescence spectra of doxorubicin in aqueous solution by femtosecond fluorescence spectroscopy

Author

Pascale Changenet-Barret, Dimitra Markovitsi, Thomas Gustavsson, Ilse Manet, Sandra Monti, Laboratoire Francis PERRIN (LFP - URA 2453), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)

Subjects
Time Factors, Dimer, General Physics and Astronomy, Quantum yield, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence spectroscopy, NUCLEAR-MAGNETIC-RESONANCE, POLAR SOLVATION DYNAMICS, DNA TOPOISOMERASE-II, SELF-ASSOCIATION, DRUG-DELIVERY, ANTHRACYCLINE ACTIVITY, CIRCULAR-DICHROISM, CHARGE SEPARATION, UP-CONVERSION, BINDING, chemistry.chemical_compound, Physical and Theoretical Chemistry, Photons, Chemistry, Lasers, Water, 021001 nanoscience & nanotechnology, Internal conversion (chemistry), Fluorescence, 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Spectrometry, Fluorescence, Resonance fluorescence, Doxorubicin, Femtosecond, 0210 nano-technology, Dimerization, Fluorescence anisotropy
Abstract

International audience; Doxorubicin (DOX) is a potent anti-tumoral agent widely used for cancer therapy. Despite numerous studies, the fluorescence properties of DOX, usually exploited for the characterization of the interaction with biological media, have until now led to controversial interpretations, mainly due to self-association of the drug in aqueous solution. We present here the first femtosecond study of DOX based on measurements with the fluorescence up-conversion technique in combination with time-correlated single photon counting using the same laser source. We provide evidence that fluorescence signals of DOX stem from monomers and dimers. DOX dimerization induces a dramatic decrease in the fluorescence quantum yield from 3.9 × 10−2 to 10−5 associated with the red shift of the fluorescence spectrum by [similar]25 nm. While the fluorescence lifetime of the monomer is 1 ns, the dimer fluorescence is found to decay with a lifetime of about 2 ps. In contrast to monomers, the fluorescence anisotropy of dimers is found to be negative. These experimental observations are consistent with an ultrafast internal conversion (

Published
2013
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15. Near-Infrared Room Temperature Emission from a Novel Class of Ru(II) Heteroleptic Complexes with Quinonoid Organometallic Linker

Author

Marie Noelle Rager, Hani Amouri, Anny Jutand, Andrea Barbieri, Aurélie Damas, Maria Pia Gullo, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Architectures Moléculaires (A.R.C), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Consiglio Nazionale delle Ricerche (CNR), École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris)

Subjects
Inorganic chemistry, design, transition-metal-complexes, chemistry.chemical_element, polypyridine complexes, 010402 general chemistry, Ligands, 01 natural sciences, 7. Clean energy, Catalysis, Ruthenium, octahedral bimetallic assemblies, Coordination Complexes, Materials Chemistry, Organometallic Compounds, [CHIM]Chemical Sciences, photophysical properties, absorption-spectra, electrochemical-behavior, Spectroscopy, Near-Infrared, luminescence properties, 010405 organic chemistry, Ligand, Near-infrared spectroscopy, Metals and Alloys, Quinones, Temperature, General Chemistry, ray molecular-structure, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Octahedron, chemistry, Ceramics and Composites, Electronics, Luminescence, Linker, Oxidation-Reduction
Abstract

WOS:000317352600022; A novel class of luminescent octahedral ruthenium complexes 2-4 displaying a pi-bonded quinonoid ligand is described. Remarkably, the presence of this organometallic ligand affects their UV-vis properties and transforms them into panchromatic absorbers. Furthermore, it turns on room temperature NIR emissions.

Published
2013
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16. Turning on Red and Near-Infrared Phosphorescence in Octahedral Complexes with Metalated Quinones

Author

Aurélie Damas, Barbara Ventura, Hani Amouri, Alessandra Degli Esposti, Andrea Barbieri, Lise-Marie Chamoreau, Jamal Moussa, Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Architectures Moléculaires (A.R.C), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche, Viale dell'Università, Glycochimie Organique Biologique et Supramoléculaire (GOBS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Stereochemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Rhodium, Ruthenium, Inorganic Chemistry, chemistry.chemical_compound, TRISPHAT, chemistry, Octahedron, Luminophore, [CHIM]Chemical Sciences, Iridium, Physical and Theoretical Chemistry, DENSITY-FUNCTIONAL THEORY, SUPRAMOLECULAR TRIANGULAR HOSTS, MEDIATED ASYMMETRIC CHEMISTRY, EXCITED-STATE PROPERTIES, COORDINATION-COMPOUNDS, CYCLOMETALATED IRIDIUM(III), Phosphorescence, Bimetallic strip
Abstract

We report the synthesis of pi-bonded ruthenium, rhodium, and iridium o-benzoquinones [Cp*M(o-C6H4O2)](n) [M = Ru (2), n = 1-; Rh (3), n = 0; Ir (4), n = 0] following a novel synthetic procedure. Compounds 2-4 were fully characterized by spectroscopic methods and used as chelating organometallic linkers, "OM-linkers", toward luminophore bricks such as Ru(bpy)(2)(2+), Rh(ppy)(2)(+), and Ir(ppy)(2)(+) (bpy = 2,2'-bipyridine; ppy = 2-phenylpyridine) for the design of a novel family of octahedral bimetallic complexes of the general formula [(L-L)(2)M(OM-linkers)[X](m) (X = counteranion; m = 0, 1, 2) whose luminescent properties depend on the choice of the OM-linker and the luminophore brick. Thus, dinuclear assemblies such as [(bpy)(2)Ru(2)][OTf] (5-OTf), [(bpy)(2)Ru(2)][Delta-TRISPHAT] (5-Delta T) {TRISPHAT = tris[tetrachlorobenzene-1,2-bis(olato)]phosphate}, [(bpy)(2)Ru(3)] [OTf](2) (6-OTf), [(bpy)(2)Ru(4)] [OTf](2) (7-OTf), [(bpy)(2)Ru(4)][Delta-TRISPHAT](2) (7-Delta T), [(ppy)(2)Rh(2)] (8), [(ppy)(2)Rh(3)][OTf] (9-OTf), [(ppy)(2)Rh(4)][OTf] (10-OTf), [(ppy)(2)Rh(4)[Delta-TRISPHAT] (10-Delta T), [(ppy)(2)Ir(2)] (11), [(ppy)(2)Ir(3)][OTf] (12-OTf), [(ppy)(2)Ir(4)][OTf] (13-OTf), and [(ppy)(2)Ir(4)][Delta-TRISPHAT] (13-Delta T) were prepared and fully characterized. The X-ray molecular structures of three of them, i.e., 5-OTf, 8, and 11, were determined. The structures displayed a main feature: for instance, the two oxygen centers of the OM-linker [Cp*Ru(o-C6H4O2)](-) (2) chelate the octahedral chromophore metal center, whether it be ruthenium, rhodium, or iridium. Further, the carbocycle of the OM-linker 2 adopts a eta(4)-quinone form but with some catecholate contribution due to metal coordination. All of these binuclear assemblies showed a wide absorption window that tailed into the near-IR (NIR) region, in particular in the case of the binuclear ruthenium complex 5-OTf with the anionic OM-linker 2. The latter feature is no doubt related to the effect of the OM-linker, which lights up the luminescence in these homo- and heterobinuclear compounds, while no effect has been observed on the UV-visible and emission properties because of the counteranion, whether it be triflate (OTf) or Delta-TRISPHAT. At low temperature, all of these compounds become luminescent; remarkably, the o-quinonoid linkers [Cp*M(o-C6H4O2)](n) (2-4) turn on red and NIR phosphorescence in the binuclear octahedral species 5-7. This trend was even more observable when the ruthenium OM-linker 2 was employed. These assemblies hold promise as NIR luminescent materials, in contrast to those made from organic 1,2-dioxolene ligands that conversely are not emissive.

Published
2012
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17. Activation of aliphatic C-H bonds by tetracyanobenzene photosensitization. A time-resolved and steady-state investigation

Author

Protti, Stefano, Fagnoni, Maurizio, Monti, Sandra, Rehault, Julien, Poizat, Olivier, Albini, Angelo, PhotoGreen Lab, Department of Chemistry, University of Pavia, Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Physikalisch-Chemisches Institut [Zürich], Universität Zürich [Zürich] = University of Zurich (UZH), Università degli Studi di Pavia = University of Pavia (UNIPV), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)

Subjects
Cyclohexane, 010405 organic chemistry, General Chemical Engineering, Radical, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Chemical reaction, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Electron transfer, Radical ion, chemistry, Flash photolysis, Molecule, Triethylamine
Abstract

The photochemistry of 1,2,4,5-tetracyanobenzene (TCB) in acetonitrile in the presence of representative aliphatic donors (cyclohexane, 1,4-dioxane and triethylamine) has been investigated by femtosecond (fs) and nanoseconds (ns) flash photolysis as well as steady state irradiation in order to define the kinetic frame for the activation of aliphatic C-H bonds. Unlike in the case of aromatics, no ground state complex (except possibly in the case of triethylamine) or exciplex is formed. The lowest excited singlet is quenched and forms the free radical ions. The efficiency of the process, measured by the yield of TCB˙− (0.84 with cyclohexane, 0.15 with 1,4-dioxane, 0.37 with triethylamine) depends on the rate of return electron transfer, low for a high exothermicity. The chemical reaction following the electron transfer step depends on the properties of the radical cation. Thus, with cyclohexane deprotonation is slow and does not occur measurably on a microsecond scale, while on a longer time scale, the formation of alkyl radicals competes with back electron transfer between the free ions. The deprotonation of amine radical cations is faster and the resulting α-aminoalkyl radicals reduce a further molecule of TCB, causing the accumulation of the radical anion which is indefinitely stable in the absence of oxygen.

Published
2012
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18. Organometallic Quinonoid Linkers: A Versatile Tether for the Design of Panchromatic Ruthenium(II) Heteroleptic Complexes

Author

Barbara Ventura, Alessandra Degli Esposti, Lise-Marie Chamoreau, M. Rosa Axet, Andrea Barbieri, Hani Amouri, Aurélie Damas, Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), departament de quimica fisica i quimica inorganica i quimica analitica i quimica organica, Universitat Rovira i Virgili, Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), IRPPS-CNR, Salerno, Università degli Studi di Salerno (UNISA), Architectures Moléculaires (A.R.C), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Salerno = University of Salerno (UNISA), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Photochemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Ruthenium, Panchromatic film, Inorganic Chemistry, OCTAHEDRAL BIMETALLIC ASSEMBLIES, SENSITIZED SOLAR-CELLS, [CHIM]Chemical Sciences, Density functional theory, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

The synthesis, X-ray structure determination, and photophysical investigation of a novel series of heteroleptic ruthenium(II) polypyridine complexes with organometallic linkers are reported. The displayed panchromatic absorption features are assigned by means of time-dependent density functional theory studies.

Published
2010
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19. The electronic properties of a homoleptic bisphosphine Cu(I) complex A joint theoretical and experimental insight

Author

Adrien Kaeser, Alessandra Degli Esposti, Jean-François Nierengarten, Gianluca Accorsi, Michel Holler, Béatrice Delavaux-Nicot, Nicola Armaroli, Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), Consiglio Nazionale delle Ricerche (CNR), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire (LCM), and Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Valence (chemistry), 010405 organic chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Biochemistry, 0104 chemical sciences, DENSITY-FUNCTIONAL THEORY, MOLECULAR-ORBITAL METHODS, EFFECTIVE CORE POTENTIALS, TRANSITION-METAL CATIONS, S/D EXCITATION-ENERGIES, PHOTOPHYSICAL PROPERTIES, COPPER(I) COMPLEXES, BASIS-SET, ADJUSTABLE-PARAMETERS, DIPHOSPHINE LIGANDS, chemistry.chemical_compound, Crystallography, chemistry, Computational chemistry, Excited state, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Singlet state, Physical and Theoretical Chemistry, Homoleptic, Triplet state, Lone pair, Basis set, Natural bond orbital
Abstract

The origin of the optical properties of the firstly reported stable luminescent [ Cu ( PP ) 2 ] + complex [ Cu ( dppb ) 2 ] + [ dppb = 1 , 2 - bis ( diphenylphosphino ) benzene ] is investigated using the exchange–correlation functional PBE0. The choice of the basis set used is discussed and a comparison with the results obtained by other functionals is performed. The role played by the bisphosphine ligands within the complex is elucidated by considering the electronic properties of the ligand alone to evidence how both the geometrical changes and the electronic interactions, induced by the inclusion of the metal cation, affect the electronic behavior of the whole system. The NBO analysis shows how the aryl groups of the ligands act as a reservoir of electrons within the complex. The electronic excitations of both the complex and of the ligand, calculated by including the solvation effects, allow to assign the lowest energy absorption broad band, recorded in CH 2 Cl 2 solution. The peculiar contribution of the phosphorus atoms to the description of the high occupied MOs and the participation of the copper cation to the description of the lowest singlet excited state, is pointed out. The origin of the observed phosphorescence of the complex is attributed to a triplet state, whose SOMO is characterized by the contributions of the valence 4 s and of the Rydberg 5 s AOs of the metal cation, along with the lone pair orbitals of the P atoms.

Published
2010
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