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

Authors :
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.
Armaroli, N.
Source :
European journal of inorganic chemistry, (2019): 2665–2673. doi:10.1002/ejic.201900335, info:cnr-pdr/source/autori:Nierengarten, Jean-Francois; Nierengarten, Iwona; Holler, Michel; Sournia-Saquet, Alix; Delavaux-Nicot, Beatrice; Leoni, Enrico; Monti, Filippo; Armaroli, Nicola/titolo:Dinuclear Copper(I) Complexes Combining Bis(diphenylphosphanyl)acetylene with 1,10-Phenanthroline Ligands/doi:10.1002%2Fejic.201900335/rivista:European journal of inorganic chemistry (Print)/anno:2019/pagina_da:2665/pagina_a:2673/intervallo_pagine:2665–2673/volume, European Journal of Inorganic Chemistry, European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2019, 2019 (22), pp.2665-2673. ⟨10.1002/ejic.201900335⟩, European Journal of Inorganic Chemistry, 2019, 2019 (22), pp.2665-2673. ⟨10.1002/ejic.201900335⟩
Publication Year :
2019
Publisher :
Wiley-VCH-Verl., Weinheim , Germania, 2019.

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).

Details

Language :
English
ISSN :
14341948 and 10990682
Database :
OpenAIRE
Journal :
European journal of inorganic chemistry, (2019): 2665–2673. doi:10.1002/ejic.201900335, info:cnr-pdr/source/autori:Nierengarten, Jean-Francois; Nierengarten, Iwona; Holler, Michel; Sournia-Saquet, Alix; Delavaux-Nicot, Beatrice; Leoni, Enrico; Monti, Filippo; Armaroli, Nicola/titolo:Dinuclear Copper(I) Complexes Combining Bis(diphenylphosphanyl)acetylene with 1,10-Phenanthroline Ligands/doi:10.1002%2Fejic.201900335/rivista:European journal of inorganic chemistry (Print)/anno:2019/pagina_da:2665/pagina_a:2673/intervallo_pagine:2665–2673/volume, European Journal of Inorganic Chemistry, European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2019, 2019 (22), pp.2665-2673. ⟨10.1002/ejic.201900335⟩, European Journal of Inorganic Chemistry, 2019, 2019 (22), pp.2665-2673. ⟨10.1002/ejic.201900335⟩
Accession number :
edsair.doi.dedup.....35547f32ac04651da76c554e4391c601
Full Text :
https://doi.org/10.1002/ejic.201900335