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3 results on '"Delavaux-Nicot B"'

1. 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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2. 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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3. 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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