Subtle Modulation of Cu4X4L2 Phosphine Cluster Cores Leads to Changes in Luminescence

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• 作者：Kelly Chen ; Jason Shearer ; Vincent J. Catalano
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 6, 2015
• 年：2015
• 卷：54
• 期：13
• 页码：6245-6256
• 全文大小：593K
• ISSN：1520-510X

文摘

A series of Cu₄X₄(PPh₂py)₂ compounds (X = Cl (1), Br (2), I (3), PPh₂py = 2-(diphenylphosphino)pyridine) were prepared and characterized using X-ray crystallography, NMR, UV鈥搗is, and luminescence spectroscopy. The copper chloride and bromide clusters have Cu₄X₄ octahedral cores while the copper iodide clusters contain an unprecedented butterfly shaped core. Crystallization of the copper bromide and iodide clusters from the appropriate solvent produced the solvates 2路2CH₂Cl₂, 2路2CHCl₃, and 3路0.5CH₂Cl₂ where the presence of the lattice solvate influences the overall structural properties. Using TD-DFT calculations, the emission was assigned to a mixed metal- and halide-to-ligand charge transfer, (M + X)LCT. Subtle differences in the copper core geometry and 渭-halide bonding perturb the emissions of these copper(I) halide clusters.