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Syntheses, Crystal Structures and Magnetic Properties of a Series of Luminescent Lanthanide Complexes Containing Neutral Tetradentate Phenanthroline-amide Ligands

Abstract

A series of lanthanide (Ln) compounds, [EuIII(L)2(MeOH)(H2O)](ClO4)3 (1), [TbIII(L)2(H2O)](Cl3) (2) and [MIII(L)2(NO3)](ClO4)2 (M = Eu (3); Sm (4); Tb (5); Dy (6)) have been prepared by treatment of the neutral tetra-dentate ligand (N2,N9-dibutyl-1,10-phenanthroline-2,9-dicarboxamide, L) with various Ln(III) salts in MeOH. All of the compounds have been structurally characterized by X-ray crystallography. It is noted that the anions of the Ln(III) salts play crucial roles in the solid state structures and properties of the resulting complexes. Compounds 1 and 2 are synthesized from the perchlorate chloride salts and the metal centres are 10- and 9-coordinated by two L ligands and solvent molecules. When the nitrate salts are used instead, four isostructural 10-coordinate Ln(III) compounds are obtained. The photophysical properties show that most of compounds exhibit the characteristic emission peaks of Ln(III). The ligand L is a very good ‘antenna’ to sensitize the Eu(III) emission, but not for the other Ln(III). The quantum yield of 3 is 75.4%, which is much higher than that of 1 (17.6%) due to the –OH oscillators of the coordinated H2O and MeOH molecules in 1. The magnetic properties of the Tb(III) compounds 2 and 5, and the Dy(III) compound 6 were investigated in detail as a natural extension of our previous study of the effect of high-coordination number on the single-ion magnet (SIM) behaviour of 3d-compounds. The results show that subtle changes of the coordination environment have significant effects on the magnetic behaviour. The 9-coordinate compound 2 is not a single ion magnet (SIM), but both 10-coordinate compounds 5 and 6 exhibit field-induced SIM behaviour. It is also interesting to note that, upon the application of a small dc field, 5 exhibits two distinct relaxation processes, which is uncommon in Ln-based SIMs.

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Publication details

The article was received on 12 Mar 2019, accepted on 11 Apr 2019 and first published on 12 Apr 2019


Article type: Research Article
DOI: 10.1039/C9QI00238C
Citation: Inorg. Chem. Front., 2019, Accepted Manuscript

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    Syntheses, Crystal Structures and Magnetic Properties of a Series of Luminescent Lanthanide Complexes Containing Neutral Tetradentate Phenanthroline-amide Ligands

    J. Xiang, Q. Su, K. Fan, X. Jin, X. Huang, S. Cheng, L. Luo, Y. Li, C. Ko, L. Zheng and T. Lau, Inorg. Chem. Front., 2019, Accepted Manuscript , DOI: 10.1039/C9QI00238C

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