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Issue 10, 2018
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Effect of ligand substitution on the SMM properties of three isostructural families of double-cubane Mn4Ln2 coordination clusters

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Abstract

Three isostructural lanthanide series with a core of MnIII2MnII2Ln2 are reported. These three families have the formulae of [MnIII2MnII2Ln24-O)2(H2edte)2(piv)6(NO3)2] {no crystallization solvent, Ln = La, Ce, Pr, Nd, Eu (1–4, 6); solv = 3MeCN, Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y (5, 7–13)}, where H2edte = N,N,N′,N‘-tetrakis(2-hydroxyethyl)ethylenediamine and piv = pivalate; [MnIII2MnII2Ln24-O)2(H2edte)2(benz)6(NO3)2], where benz = benzoate, or [MnIII2MnII2Ln24-O)2(edteH2)2(benz)6(NO3)2]·2MeCN {Ln = Gd, Tb, Dy (14–16); and [MnIII2MnII2Ln24-O)2(edteH2)2(piv)8].solv {solv = 4MeCN, Ln = La (17); solv = 2MeCN·tol·H2O, Ln = Pr, Nd, Sm, Tb (18–20, 22); solv = 2MeCN·H2O, Ln = Gd (21). These compounds crystallize in two different systems, namely, monoclinic in the space groups P21/n for 1–4, 6, and 14–16 and C2/c for 5, 7–13, 18–20, and 22 and triclinic in the space group P[1 with combining macron] for 17 and 21. The crystal structures of these compounds display a face-fused dicubane structure connected by different types of bridged oxygen atoms. Solid-state dc magnetic susceptibility characterization was carried out for 1–22, and fitting showed that MnIII⋯MnIII is antiferromagnetically (AF) coupled and MnII⋯MnIII, MnII⋯Ln and MnIII⋯Ln are weakly ferromagnetically coupled. In addition, ac measurements were carried out and showed that only 7, 15, and 22 for Tb, 8 and 16 for Dy, and 20 for Sm exhibited slow magnetization relaxation. In the case of 15, it was possible to determine the energy barrier of the slow-relaxation behavior by fitting peak temperatures to the Arrhenius law, which gave a value of Ueff = 21.2 K and a pre-exponential factor of τ0 = 4.0 × 10−9 s.

Graphical abstract: Effect of ligand substitution on the SMM properties of three isostructural families of double-cubane Mn4Ln2 coordination clusters

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Publication details

The article was received on 14 Nov 2017, accepted on 24 Jan 2018 and first published on 24 Jan 2018


Article type: Paper
DOI: 10.1039/C7DT04304J
Citation: Dalton Trans., 2018,47, 3485-3495
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    Effect of ligand substitution on the SMM properties of three isostructural families of double-cubane Mn4Ln2 coordination clusters

    M. N. Akhtar, Y. Lan, M. A. AlDamen, Y. Zheng, C. E. Anson and A. K. Powell, Dalton Trans., 2018, 47, 3485
    DOI: 10.1039/C7DT04304J

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