Separation of Geometric Isomers of a Dicopper Complex by Using a 19F-Labeled Ligand: Dynamics, Structures, and DFT Calculations

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• 作者：Stphanie Durot ; Laila H. Hossain ; Sylvain Hamman ; Hlne Jamet ; Maylis Orio ; Isabelle Gautier-Luneau ; Dominique Luneau ; Christian Philouze ; Jean-Louis Pierre ; Catherine Belle
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：September 6, 2010
• 年：2010
• 卷：49
• 期：17
• 页码：7832-7840
• 全文大小：899K
• 年卷期：v.49,no.17(September 6, 2010)
• ISSN：1520-510X

文摘

Introducing a fluorine group on two pyridines of the HL_CH3 ligand (2,6-bis[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol) allows the separation of two geometric isomers after complexation by two copper(II) ions. Methods for isolating the isomers (1_meso and 1_rac) as a μ-phenoxo,μ-hydroxo dicopper(II) complex as a crystalline product have been developed. Both isomers (1_meso and 1_rac) have been characterized by X-ray crystallography and ¹⁹F NMR. The isomerism is determined by the disposition of the fluorine atoms with respect to the plane containing the Cu₂O₂ core. Density functional theory calculations using different functionals were performed to provide additional support for the existence of these two forms. Dissolution of 1_meso in acetone or acetonitrile causes its spontaneous isomerization into the 1_rac form at room temperature. Combined experimental studies (UV−vis, ¹⁹F NMR) and theoretical calculations support this process. Paramagnetic ¹⁹F NMR appears as a unique and powerful probe for distinguishing the two isomers and supplying direct evidence of this isomerization process in solution.