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

1. 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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2. 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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3. 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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4. 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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5. 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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6. 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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7. 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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8. Induced phosphorescence from Pt → Ag and Ag( \textlessspan style='font-variant:small-caps;'\textgreateri\textless/span\textgreater )⋯Ag( \textlessspan style='font-variant:small-caps;'\textgreateri\textless/span\textgreater ) metallophilic interactions in benzenedithiolatodiimine-Pt _\textrm2 /Ag _\textrm2 clusters: a combined experimental and theoretical investigation

Author

Moussa, Jamal, Chamoreau, Lise Marie, Gullo, Maria Pia, Degli Esposti, Alessandra, Barbieri, Andrea, Amouri, Hani, 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
[CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; no abstract

Published
2016
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9. A unique class of neutral cyclometalated platinum( \textlessspan style='font-variant:small-caps;'\textgreaterii\textless/span\textgreater ) complexes with π-bonded benzenedithiolate: synthesis, molecular structures and tuning of luminescence properties

Author

Sesolis, Hugo, Moussa, Jamal, Gontard, Geoffrey, Jutand, Anny, Gullo, Maria Pia, Barbieri, Andrea, Amouri, Hani, 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), 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), 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), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), and Consiglio Nazionale delle Ricerche (CNR)

Subjects
[CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; no abstract

Published
2015
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10. International benchmark on the natural convection test in Phenix reactor

Author

Hiroyasu Mochizuki, Aurélia Chenu, Y. Shvetsov, L. Maas, T. H. Fanning, Stefano Monti, D. Pialla, H.-Y. Jeong, J. W. Thomas, Konstantin Mikityuk, D. Tenchine, P. Chellapandi, Service de Thermo-hydraulique et de Mécanique des Fluides (STMF), Département de Modélisation des Systèmes et Structures (DM2S), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Argonne National Laboratory [Lemont] (ANL), Nuclear and Radioanalytical Chemistry, IGCAR, Kalpakkam-603102, Tamilnadu, Institut de Radioprotection et de Sûreté Nucléaire (IRSN), Korea Atomic Energy Research Institute [Daejeon, south Korea] (KAERI), Paul Scherrer Institute (PSI), University of Fukui [Bunkyo], Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), International Atomic Energy Agency [Vienna] (IAEA), and Consiglio Nazionale delle Ricerche (CNR)

Subjects
Nuclear and High Energy Physics, Engineering, Russian federation, Sensitivity studies, 020209 energy, Shutdown, Nuclear engineering, Control rod, Testing, Mechanical engineering, 02 engineering and technology, Scram, 01 natural sciences, 7. Clean energy, 010305 fluids & plasmas, Blind calculations, Sodium-cooled fast reactor, Benchmark (surveying), 0103 physical sciences, 0202 electrical engineering, electronic engineering, information engineering, General Materials Science, Natural circulation, Safety, Risk, Reliability and Quality, Waste Management and Disposal, Sodium cooled fast reactors (SFR), [PHYS]Physics [physics], Natural convection, business.industry, Mechanical Engineering, Sodium, Test (assessment), Fast reactors, Nuclear Energy and Engineering, Primary circuits, 13. Climate action, business, Coordinated research projects, International atomic energy agency
Abstract

The French Phenix sodium cooled fast reactor (SFR) started operation in 1973 and was stopped in 2009. Before the reactor was definitively shutdown, several final tests were planned and performed, including a natural convection test in the primary circuit. During this natural convection test, the heat rejection provided by the steam generators was disabled, followed several minutes later by reactor scram and coast-down of the primary pumps. The International Atomic Energy Agency (IAEA) launched a Coordinated Research Project (CRP) named "control rod withdrawal and sodium natural circulation tests performed during the Phenix end-of-life experiments". The overall purpose of the CRP was to improve the Member States' analytical capabilities in the field of SFR safety. An international benchmark on the natural convection test was organized with "blind" calculations in a first step, then "post-test" calculations and sensitivity studies compared with reactor measurements. Eight organizations from seven Member States took part in the benchmark: ANL (USA), CEA (France), IGCAR (India), IPPE (Russian Federation), IRSN (France), KAERI (Korea), PSI (Switzerland) and University of Fukui (Japan). Each organization performed computations and contributed to the analysis and global recommendations. This paper summarizes the findings of the CRP benchmark exercise associated with the Phenix natural convection test, including blind calculations, post-test calculations and comparisons with measured data. General comments and recommendations are pointed out to improve future simulations of natural convection in SFRs. © 2013 Elsevier B.V.

Published
2013
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11. 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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12. 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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13. 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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14. 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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15. 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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