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