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Issue 33, 2011
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A dinuclear extension to constrained heteroleptic Cu(I) systems

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This article reports the synthesis and optical properties of three dinuclear, cationic copper complexes [Cu2(μ-dppm)2(μ-L)](NO3)2 (dppm diphenyldiphosphinomethane, L: LA 3,6-bis(2-pyridyl)-4,5-diphenyl-pyridazine, LB 3,6-bis(2-pyridyl)-4,5-di(4-pyridyl)-pyridazine and LC 3,6-bis(2-pyridyl)-8,9-diazafluoranthene). These were formed on the reaction of [Cu(μ-dppm)(NO3)]2 with a series of N-donor (bppn) ligands L. The single crystal X-ray structures of [Cu2(μ-dppm)2(μ-L)](NO3)2·CH2Cl2 were determined and revealed that in both, the two copper atoms are held by three bridging ligands, two dppm ligands and one bppn ligand acting as a tetradentate bridge. The absorption spectra of the complexes present a MLCT [Cu →π*(NN)] band in the λ 370–425 nm region. These new complexes exhibit red-orange MLCT-based emission in the solid-state with lifetimes in the microsecond range. In oxygen-free dichloromethane solution, the complex [Cu2(μ-dppm)2(μ-LC)]2+ has a long lifetime of 22.8 μs. The long emission lifetimes are attributed to a rigid conformation that precludes the possible distortion of the copper in the excited state.

Graphical abstract: A dinuclear extension to constrained heteroleptic Cu(i) systems

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The article was received on 18 Feb 2011, accepted on 13 May 2011 and first published on 12 Jul 2011

Article type: Paper
DOI: 10.1039/C1DT10275C
Citation: Dalton Trans., 2011,40, 8320-8327
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    A dinuclear extension to constrained heteroleptic Cu(I) systems

    B. Gil, G. A. Cooke, D. Nolan, G. M. Ó Máille, S. Varughese, L. Wang and S. M. Draper, Dalton Trans., 2011, 40, 8320
    DOI: 10.1039/C1DT10275C

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