Synthesis, structures and photoluminescent properties of Cu+ complexes with extended π-systems

Yin, Guodong; Lian, Heng-Chi; Ni, Qing-Ling; Gui, Liu-Cheng; Yang, Kun-Guo; Wang, Xiu-Jian

doi:10.1016/j.inoche.2012.05.005

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References 11 publications

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“…The Cu–P bond distances are in the range of 2.250(1)–2.260(1) Å, except for Cu(2)–P(3) with a longer distance of 2.280(1) Å, indicating the effect of larger steric hindrance and/or ligand field splitting due to CH 3 CN than water. The Cu–N bond distances between the Cu centers and the MeOpyz ligand (2.070(4)–2.098(4) Å) are similar to those reported for pyrazine-bridged Cu(I) complexes. , The Cu(2)–N(3) bond distance of 2.032(5) Å in H 2 O–Cu 2 –AN is also similar to that in the starting material [Cu(CH 3 CN) 4 ](BF 4 ). It is noteworthy that the Cu–O distance in H 2 O–Cu 2 –AN is considerably longer by ∼0.04 Å than that in H 2 O–Cu 2 –H 2 O , although these Cu–O bond distances are short enough to make coordination bonds considering the sum of the ionic radius of Cu(I) and O 2– ions (2.36 Å).…”

Section: Resultssupporting

confidence: 78%

“…The Cu−P bond distances are in the range of 2.250(1)−2.260(1) Å, except for Cu(2)−P(3) with a longer distance of 2.280(1) Å, indicating the effect of larger steric hindrance and/or ligand field splitting due to CH 3 CN than water. The Cu−N bond distances between the Cu centers and the MeOpyz ligand (2.070(4)−2.098(4) Å) are similar to those reported for pyrazine-bridged Cu(I) complexes 39,52. The Cu(2)−N(3) bond distance of 2.032(5) Å in H 2 O−Cu 2 −AN is also similar to that in the starting material [Cu(CH 3 CN) 4 ]-(BF 4 ).…”

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confidence: 78%

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Effect of Water Coordination on Luminescent Properties of Pyrazine-Bridged Dinuclear Cu(I) Complexes

et al. 2017

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Two luminescent pyrazine-bridged dinuclear Cu(I) complexes, namely, [{Cu(PPh)(HO)}(μ-MeOpyz){Cu(PPh)(CHCN)}](BF) and [{Cu(PPh)(HO)}(μ-MeOpyz){Cu(PPh)(HO)}](BF) (HO-Cu-AN and HO-Cu-HO; PPh = triphenylphosphine, MeOpyz = 2-methoxypyrazine), were successfully synthesized and characterized by single-crystal X-ray diffraction and luminescence measurements. X-ray analysis revealed that the water molecules are coordinated to both Cu(I) ions to form almost the same PNO coordination structure in HO-Cu-HO, whereas one of the two Cu ions in HO-Cu-AN was coordinated by acetonitrile instead of water to form a different PN coordination environment. The asymmetric HO-Cu-AN exhibits very bright yellow-green emission with a high emission quantum yield (λ = 550 nm, Φ = 0.70) at room temperature in the solid state in spite of the coordination of water molecule, which usually tends to deactivate the emissive state through O-H vibration. The intense emission at room temperature is a result of thermally activated delayed fluorescence, and the remarkable temperature dependence of emission lifetimes indicates the existence of unique multiple emission states for the asymmetric dinuclear complex. In contrast, the emission of HO-Cu-HO was observed at longer wavelengths with remarkably a lower quantum yield (λ = 580 nm, Φ = 0.05). Time-dependent density functional theory calculations suggested that the emission could result from the metal-to-ligand charge-transfer transition state. However, it could be rapidly deactivated by the structural distortion around the Cu ion with a less-bulky coordination environment in HO-Cu-HO.

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Section: Resultssupporting

confidence: 78%

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confidence: 78%