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Chiral six-coordinate Dy(III) and Tb(III) complexes of an achiral ligand: structure, fluorescence, and magnetism

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Abstract

Two new chiral six-coordinate lanthanide complexes (1 for Dy and 2 for Tb) have been synthesized using the achiral flexible ligand H2L (2,2′-[1,2-ethanediylbis[(methylimino)methylene]]bis[4,5-dimethylphenol]). Both complexes crystallize in the chiral P1 group space, and the enantiomers [Zn(L)Cl]3Dy·MeOH·0.5H2O (Λ-1), [Zn(L)Cl]3Dy·1.5H2O (Δ-1), [Zn(L)Cl]3Tb·1.5H2O (Λ-2) and [Zn(L)Cl]3Tb·H2O (Δ-2) are isolated in the reaction. Three [Zn(L)Cl] anions coordinate to the central lanthanide ion using two phenoxo oxygen atoms of L2−, and the lanthanide ion has the coordination geometry of D3. Complex 1 exhibits a field-induced slow magnetization relaxation, which is typical of a single-ion magnet (SIM). Ab initio calculations on complex 1 and studies on magneto-structural correlationship of six-coordinate Dy(III) SIMs indicate that the small energy barrier of complex 1 might be related to the absence of a unique anisotropic axis for the regular octahedral coordination configuration of Dy(III) and the high quantum tunneling gap between the ground states (mJ = ±15/2). Complex 2 displays green photofluorescence and triboluminescence.

Graphical abstract: Chiral six-coordinate Dy(iii) and Tb(iii) complexes of an achiral ligand: structure, fluorescence, and magnetism

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Publication details

The article was received on 04 Jul 2017, accepted on 08 Sep 2017 and first published on 11 Sep 2017


Article type: Paper
DOI: 10.1039/C7DT02409F
Citation: Dalton Trans., 2017, Advance Article
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    Chiral six-coordinate Dy(III) and Tb(III) complexes of an achiral ligand: structure, fluorescence, and magnetism

    M. Liu, J. Yuan, Y. Zhang, H. Sun, C. Liu and H. Kou, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02409F

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