Dinuclear Cu(I) complexes prepared from 2-diphenylphosphino-6-methylpyridine

J. J. Cid, J. Mohanraj, M. Mohankumar, M. Holler, F. Monti, G. Accorsi, L. Karmazin-Brelot, I. Nierengarten, J. M. Malicka, M. Cocchi, B. Delavaux-Nicot, N. Armaroli, J. F. Nierengarten

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


A series of reactions have been performed by mixing 2-diphenylphosphino-6-methyl-pyridine (dpPyMe) and [Cu(CH3CN)4]BF4 in different molar ratios. Starting from equimolar quantities of dpPyMe and Cu+, a dinuclear Cu(I) complex with two P,N binucleating bridging ligands has been obtained. This compound is stable in the solid state, however ligand exchange reactions leading to a mixture of species have been evidenced in solution. By increasing the amount of dpPyMe, the reaction of dpPyMe and [Cu(CH3CN)4]BF4 afforded the dinuclear Cu(I) complex [Cu2(μ-dpPyMe)3(CH3CN)](BF4)2 in which the three bridging dpPyMe ligands are in a head-to-head arrangement. This compound is remarkably stable in solution. It has been also shown that the axial CH3CN ligand of [Cu2(μ-dpPyMe)3(CH3CN)](BF4)2 can be suitably exchanged with other nitrile ligands [benzonitrile, 4-(dimethylamino)-benzonitrile, 4-nitrobenzonitrile and bromoacetonitrile] but also with triphenylphosphine oxide. The electrochemical and photophysical properties of the resulting complexes have been systematically investigated. The [Cu2(μ-dpPyMe)3(L)](BF4)2 derivatives are weak emitters in solution but remarkable emission quantum yields (6 to 46%) have been found in rigid matrices at room temperature. One complex was utilized as active material for preliminary tests in LEC devices.

Original languageEnglish
Pages (from-to)158-172
Number of pages15
StatePublished - 4 Nov 2014
Externally publishedYes

Bibliographical note

Funding Information:
This research was supported by CNRS , University of Strasbourg , MIUR (PRIN 2010 INFOCHEM, contract no. CX2TLM; FIRB Futuro in Ricerca SUPRACARBON, contract no. RBFR10DAK6), CNR (MACOL PM. P04. 010; Progetto Bandiera N-CHEM), EC (contract PITN-GA-2008-215399 - FINELUMEN), ESF-EUROCORES (10-EuroSolarFuels-FP-006, SOLARFUELTANDEM) and Consorzio MIST E-R (project FESR-Tecnopolo AMBIMAT). We further thank O. Moudam and A. Kaeser for the initial preparation of compound 1 , M. Schmitt for high field NMR measurements, A. Saquet for electrochemical measurements and D. Tordera (University of Valencia, Spain) for helpful discussions on LEC devices.

Publisher Copyright:
© 2014 Elsevier Ltd. All rights reserved.


  • Cu(I) complexes
  • LEC devices
  • Luminescence
  • Photochemistry
  • Solar energy


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