Lanthanide(III) Complexes with 4,5-Bis(diphenylphosphinoyl)-1,2,3-triazolate and the Use of 1,10-Phenanthroline As Auxiliary Ligand

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• 作者：Marisol Correa-Ascencio ; Elizabeth K. Galvn-Miranda ; Fernando Rascn-Cruz ; Omar Jimnez-Sandoval ; Sergio J. Jimnez-Sandoval ; Raymundo Cea-Olivares ; Vojtech Jancik ; R. Alfredo Toscano ; Vernica Garca-Monta
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：May 3, 2010
• 年：2010
• 卷：49
• 期：9
• 页码：4109-4116
• 全文大小：871K
• 年卷期：v.49,no.9(May 3, 2010)
• ISSN：1520-510X

文摘

New lanthanide complexes with 4,5-bis(diphenyl)phosphoranyl-1,2,3-triazolate (L⁻), LnL₃·nH₂O (1− 8) and LnL₃(phen)·nH₂O (9−16) (Ln = La, Ce, Nd, Sm, Eu, Gd, Tb, Er), have been prepared and spectroscopically characterized. The structures of LnL₃ · nH₂O (Ln = La, Ce, Nd, Sm and Gd) were determined by X-ray crystallography. The metal centers exhibit a distorted trigonal dodecahedron coordination environment with two symmetrically O,O-bidentate ligands and one unsymmetrically O,N- ligand attached to the metal; two oxygen atoms from neighboring dimethyl sulfoxide (DMSO) molecules complete the coordination sphere. This unsymmetrical ligand coordination behavior was also identified in solution through ³¹P{¹H} NMR studies. Photoluminescence spectroscopy experiments in CH₂Cl₂ for both types of complexes containing Eu(III) (6, 14) and Tb(III) (7, 15) exhibit strong characteristic red and green emission bands for Eu(III) and Tb(III), respectively. Furthermore, NdL₃ (phen)·5H ₂O (11) displays emission in the near-infrared spectral region (⁴F_3/2 → ⁴F_9/2 at 872 nm and ⁴F_3/2 → ⁴F_11/2 at 1073 nm). The complexes containing 1,10-phenantroline exhibit higher quantum yields upon excitation at 267 nm, indicating that this auxiliary ligand promotes the luminescence of the complexes; however, luminescence lifetimes (τ) in this case are shorter than those of the LnL₃·nH₂O series.