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Issue 20, 2020
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The differential magnetic relaxation behaviours of slightly distorted triangular dodecahedral dysprosium analogues in a type of cyano-bridged 3d–4f zig-zag chain compounds

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Abstract

A class of cyano-bridged 3d–4f zig-zag chain compounds, {RE[TM(CN)6] (PNO)2(H2O)4}·(H2O) {RE = YIII, TM = [FeIII]LS (1); RE = DyIII, TM = [FeIII]LS (2), CoIII (3)}, have been synthesized and characterized by single-crystal X-ray diffraction. The rare earth ions in these compounds are situated in a slightly distorted triangular dodecahedral (D2d) coordination environment. The magnetic properties of compounds 1–3 have been comparatively studied in detail. Under a zero dc field, the temperature dependence of ac susceptibility measurements for YFe (1) indicates the absence of magnetic relaxation stemming from the single anisotropic [FeIII]LS ion. The dysprosium analogue DyFe (2) shows only magnetic relaxation behavior with a prominent QTM effect, while DyCo (3) exhibits SIM properties not completely covered by QTM, with an extracted energy barrier of 73 K under a zero dc field. The ab initio calculations indicate that both compounds 2 and 3 are SMMs with well-behaved magnetic relaxation properties primarily from the individual DyIII ion. Therefore, the different magnetic behaviors exhibited by compound 2 compared to 3 may be ascribed to the stronger QTM effect caused by the extra weak interaction of [FeIII]LS ions in 2 as a fluctuating transverse field around the DyIII ion. The QTM effect for both 2 and 3 is suppressed under an applied dc field with an effective energy barrier of 134 and 150 K, respectively. Compared with compound 2, the higher extracted Ueff/kB and χ′′(T) peak temperature for 3 should be further attributed to its slightly higher single-ion axiality as calculated and the elimination of the transverse field from the [FeIII]LS ion.

Graphical abstract: The differential magnetic relaxation behaviours of slightly distorted triangular dodecahedral dysprosium analogues in a type of cyano-bridged 3d–4f zig-zag chain compounds

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Article information


Submitted
16 Mar 2020
Accepted
25 Apr 2020
First published
27 Apr 2020

Dalton Trans., 2020,49, 6867-6875
Article type
Paper

The differential magnetic relaxation behaviours of slightly distorted triangular dodecahedral dysprosium analogues in a type of cyano-bridged 3d–4f zig-zag chain compounds

A. Xue, Y. Liu, J. Li, Y. Zhang, Y. Meng, W. Zhu, Y. Zhang, H. Sun, F. Wang, G. Qiu, L. Liang, X. Wang and S. Gao, Dalton Trans., 2020, 49, 6867
DOI: 10.1039/D0DT00990C

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