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Issue 43, 2013
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Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinate lanthanide ions

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Abstract

Reaction of the chiral ligand (−)-4,5-pinenepyridyl-2-pyrazine (L) with Ln(hfac)3·2H2O precursors [hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate, Ln = Sm3+ (1), Eu3+ (2), Tb3+ (3) and Dy3+ (4)] in methanol solution led to the formation of four noncentrosymmetric lanthanide complexes with the general formula [Ln(hfac)3L]n·H2O. The single-crystal X-ray diffraction analyses revealed that they are isostructural and take a one-dimensional (1D) chain structure based on the Ln(hfac)3L repeating units, in which the nine-coordinate Ln3+ ions reside in a tricapped trigonal prism (TTP) environment never reported in previous 1D chain lanthanide complexes. The investigations of their photophysical properties showed that complexes 1, 2 and 3 exhibit characteristic emissions of Sm3+, Eu3+ and Tb3+ ions with respective luminescent lifetime values of 0.065, 1.066 and 0.129 ms, while complex 4 does not display any emission. The different luminescent intensities and lifetimes among them were further discussed in detail. Moreover, the magnetic properties of complexes 1–4 were assessed with a special emphasis on the Dy3+ complex 4. Alternating-current (ac) magnetic susceptibility measurements indicated that field-induced two-step slow magnetic relaxation processes were observed in 4, indicating the single-molecule magnet (SMM) behavior of 4. In addition, the noncentrosymmetric complexes 1–4 crystallizing in the same polar point group (Cs) exhibit both ferroelectric and nonlinear optical properties at room temperature. All these features make them multifunctional crystalline molecule materials.

Graphical abstract: Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinate lanthanide ions

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Publication details

The article was received on 29 Jun 2013, accepted on 19 Aug 2013 and first published on 19 Aug 2013


Article type: Paper
DOI: 10.1039/C3DT51743H
Citation: Dalton Trans., 2013,42, 15317-15325
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    Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinate lanthanide ions

    X. Li, C. Chen, H. Xiao, A. Wang, C. Liu, X. Zheng, L. Gao, X. Yang and S. Fang, Dalton Trans., 2013, 42, 15317
    DOI: 10.1039/C3DT51743H

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