Effects of Ligand Geometry on the Photophysical Properties of Photoluminescent Eu(III) and Sm(III) 1-Hydroxypyridin-2-one Complexes in Aqueous Solution

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• 作者：Lena J. Daumann ; David S. Tatum ; Christopher M. Andolina ; Joseph I. Pacold ; Anthony D’Aléo ; Ga-lai Law ; Jide Xu ; Kenneth N. Raymond
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：January 4, 2016
• 年：2016
• 卷：55
• 期：1
• 页码：114-124
• 全文大小：558K
• ISSN：1520-510X

文摘

A series of 10 tetradentate 1-hydroxy-pyridin-2-one (1,2-HOPO) ligands and corresponding eight-coordinated photoluminescent Eu(III) and Sm(III) complexes were prepared. Generally, the ligands differ by the linear (nLI) aliphatic linker length, from 2 to 8 methylene units between the bidentate 1,2-HOPO chelator units. The photoluminescent quantum yields (Φ_tot) were found to vary with the linker length, and the same trend was observed for the Eu(III) and Sm(III) complexes. The 2LI and 5LI bridged complexes are the brightest (Φ_totxε). The change in ligand wrapping pattern between 2LI and 5LI complexes observed by X-ray diffraction (XRD) is further supported by density functional theory (DFT) calculations. The bimodal Φ_tot trends of the Eu(III) and Sm(III) complexes are rationalized by the change in ligand wrapping pattern as the bridge (nLI) is increased in length.