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

作者：Cid J J; Mohanraj J; Mohankumar M; Holler M; Monti F; Accorsi G; Karmazin Brelot L; Nierengarten I; Malicka J M; Cocchi M; Delavaux Nicot B^*; Armaroli N; Nierengarten J F

来源：Polyhedron, 2014, 82: 158-172.

DOI：10.1016/j.poly.2014.06.009

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

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 [Cu-2(mu-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 [Cu-2(mu-dpPyMe)(3)(CH3CN)](BF4)(2) can be suitably exchanged with other nitrite ligands [benzonitrile, 4-(dimethylamino)-benzonitrile, 4-nitrobenzonitrile and bromoacetonitrilel but also with triphenylphosphine oxide. The electrochemical and photophysical properties of the resulting complexes have been systematically investigated. The [Cu-2(mu-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.

• 出版日期2014-11-4