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A Novel Luminescent Ionic Trinuclear Cu3I2 Cluster Cuprous Complex Supported By A P^N Ligand: Synthesis, Structure Characterization, Properties And TD-DFT Calculations.

Qiumeng Zhu, Li Song, Wenxiang Chai, Hangyan Shen, Qinhua Wei, Laishun Qin
Published 2018 · Chemistry, Medicine
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Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title ionic trinuclear Cu3I2 complex, tris[μ2-diphenyl(pyridin-2-yl)phosphane-κ2P:N]di-μ3-iodido-tricopper(I)(3 Cu-Cu) hexafluoridophosphate, [Cu3I2(C39H32NP)3]PF6, conventionally abbreviated as [Cu3I2(Ph2PPy)3]PF6, is described. Each CuI atom is coordinated by two μ3-iodide ligands and by a P and an N atom from two Ph2PPy ligands, giving rise to a CuI2PN tetrahedral coordination geometry about each CuI centre. The electronic absorption and photoluminescence properties of this trinuclear cluster have been studied on as-synthesized samples, which had been examined previously by powder X-ray diffraction. A detailed time-dependent density functional theory (TD-DFT) study was carried out and showed a green emission derived from a halide-to-ligand charge transfer and metal-to-ligand charge transfer 3(X+M)LCT excited state.
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