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

doi:10.1016/j.poly.2014.06.009

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

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Abstract

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 language	English
Pages (from-to)	158-172
Number of pages	15
Journal	Polyhedron
Volume	82
DOIs	https://doi.org/10.1016/j.poly.2014.06.009
State	Published - 4 Nov 2014
Externally published	Yes

Bibliographical note

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

Funding

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.

Funders	Funder number
Ministero dell’Istruzione, dell’Università e della Ricerca	CX2TLM, RBFR10DAK6
Université de Strasbourg
Consiglio Nazionale delle Ricerche
Centre National de la Recherche Scientifique

Keywords

Cu(I) complexes
LEC devices
Luminescence
Photochemistry
Solar energy

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10.1016/j.poly.2014.06.009

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title = "Dinuclear Cu(I) complexes prepared from 2-diphenylphosphino-6-methylpyridine",

abstract = "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.",

keywords = "Cu(I) complexes, LEC devices, Luminescence, Photochemistry, Solar energy",

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

year = "2014",

month = nov,

day = "4",

doi = "10.1016/j.poly.2014.06.009",

language = "אנגלית",

volume = "82",

pages = "158--172",

journal = "Polyhedron",

issn = "0277-5387",

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T1 - Dinuclear Cu(I) complexes prepared from 2-diphenylphosphino-6-methylpyridine

AU - Cid, J. J.

AU - Mohanraj, J.

AU - Mohankumar, M.

AU - Holler, M.

AU - Monti, F.

AU - Accorsi, G.

AU - Karmazin-Brelot, L.

AU - Nierengarten, I.

AU - Malicka, J. M.

AU - Cocchi, M.

AU - Delavaux-Nicot, B.

AU - Armaroli, N.

AU - Nierengarten, J. F.

PY - 2014/11/4

Y1 - 2014/11/4

N2 - 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.

AB - 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.

KW - Cu(I) complexes

KW - LEC devices

KW - Luminescence

KW - Photochemistry

KW - Solar energy

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DO - 10.1016/j.poly.2014.06.009

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AN - SCOPUS:84907890665

SN - 0277-5387

VL - 82

SP - 158

EP - 172

JO - Polyhedron

JF - Polyhedron

ER -

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

Abstract

Bibliographical note

Funding

Keywords

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