Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix Dependence
A new compound [Y<sub>2</sub>(sq)<sub>3</sub>(H<sub>2</sub>O)<sub>4</sub>] (Y-sq; sq = squarate (C<sub>4</sub>O<sub>4</sub><sup>2–</sup>)) was prepared and structurally characterized. Since the RE-sq family (RE = Y,...
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2025-01-01
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| author | Rina Takano Takayuki Ishida |
| author_facet | Rina Takano Takayuki Ishida |
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| description | A new compound [Y<sub>2</sub>(sq)<sub>3</sub>(H<sub>2</sub>O)<sub>4</sub>] (Y-sq; sq = squarate (C<sub>4</sub>O<sub>4</sub><sup>2–</sup>)) was prepared and structurally characterized. Since the RE-sq family (RE = Y, Dy, Yb, Lu) gave isostructural crystals, the objective of this study is to explore the effects of diamagnetic dilution on the SIM behavior through systematic investigation and comparison of diamagnetically diluted and undiluted forms. The 1%-Diluted Dy compounds, Dy@Y-sq and Dy@Lu-sq, showed AC magnetic susceptibility peaks without any DC bias field (<i>H</i><sub>DC</sub>), whereas undiluted Dy-sq showed no AC out-of-phase response under the same conditions. The Orbach and Raman mechanisms are assumed in the Arrhenius plots, giving <i>U</i><sub>eff</sub>/<i>k</i><sub>B</sub> = 139(5) and 135(8) K for Dy@Y-sq and Dy@Lu-sq, respectively, at <i>H</i><sub>DC</sub> = 0 Oe. In contrast, Yb@Y-sq and Yb@Lu-sq behaved different; Yb@Y-sq can be regarded as a field-induced SIM because AC out-of-phase response was recorded only when <i>H</i><sub>DC</sub> was present. On the other hand, Yb@Lu-sq showed a relaxation independent from temperature around 2 K at <i>H</i><sub>DC</sub> = 0 Oe, possibly ascribed to a quantum-tunneling-magnetization mechanism. Applying <i>H</i><sub>DC</sub> = 400 Oe afforded <i>U</i><sub>eff</sub> = 61.2(14) and 62.5(16) K for Yb@Y-sq and Yb@Lu-sq, respectively. The Y/Lu matrix dependence may be related to spin–phonon coupling. The dilution technique is a facile and versatile tool for modification of SIM characteristics. |
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| publishDate | 2025-01-01 |
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| spelling | doaj-art-184621e7bcee4980a39498929fe1741e2025-01-24T13:43:45ZengMDPI AGMolecules1420-30492025-01-0130235610.3390/molecules30020356Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix DependenceRina Takano0Takayuki Ishida1Department of Engineering Science, The University of Electro-Communications, Chofu 182-8585, Tokyo, JapanDepartment of Engineering Science, The University of Electro-Communications, Chofu 182-8585, Tokyo, JapanA new compound [Y<sub>2</sub>(sq)<sub>3</sub>(H<sub>2</sub>O)<sub>4</sub>] (Y-sq; sq = squarate (C<sub>4</sub>O<sub>4</sub><sup>2–</sup>)) was prepared and structurally characterized. Since the RE-sq family (RE = Y, Dy, Yb, Lu) gave isostructural crystals, the objective of this study is to explore the effects of diamagnetic dilution on the SIM behavior through systematic investigation and comparison of diamagnetically diluted and undiluted forms. The 1%-Diluted Dy compounds, Dy@Y-sq and Dy@Lu-sq, showed AC magnetic susceptibility peaks without any DC bias field (<i>H</i><sub>DC</sub>), whereas undiluted Dy-sq showed no AC out-of-phase response under the same conditions. The Orbach and Raman mechanisms are assumed in the Arrhenius plots, giving <i>U</i><sub>eff</sub>/<i>k</i><sub>B</sub> = 139(5) and 135(8) K for Dy@Y-sq and Dy@Lu-sq, respectively, at <i>H</i><sub>DC</sub> = 0 Oe. In contrast, Yb@Y-sq and Yb@Lu-sq behaved different; Yb@Y-sq can be regarded as a field-induced SIM because AC out-of-phase response was recorded only when <i>H</i><sub>DC</sub> was present. On the other hand, Yb@Lu-sq showed a relaxation independent from temperature around 2 K at <i>H</i><sub>DC</sub> = 0 Oe, possibly ascribed to a quantum-tunneling-magnetization mechanism. Applying <i>H</i><sub>DC</sub> = 400 Oe afforded <i>U</i><sub>eff</sub> = 61.2(14) and 62.5(16) K for Yb@Y-sq and Yb@Lu-sq, respectively. The Y/Lu matrix dependence may be related to spin–phonon coupling. The dilution technique is a facile and versatile tool for modification of SIM characteristics.https://www.mdpi.com/1420-3049/30/2/356rare earth metallanthanidesingle-ion magnetmagnetization reversalrelaxation mechanism |
| spellingShingle | Rina Takano Takayuki Ishida Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix Dependence Molecules rare earth metal lanthanide single-ion magnet magnetization reversal relaxation mechanism |
| title | Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix Dependence |
| title_full | Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix Dependence |
| title_fullStr | Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix Dependence |
| title_full_unstemmed | Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix Dependence |
| title_short | Magnetically Diluted Dy<sup>3+</sup> and Yb<sup>3+</sup> Squarates Showing Relaxation Tuning and Matrix Dependence |
| title_sort | magnetically diluted dy sup 3 sup and yb sup 3 sup squarates showing relaxation tuning and matrix dependence |
| topic | rare earth metal lanthanide single-ion magnet magnetization reversal relaxation mechanism |
| url | https://www.mdpi.com/1420-3049/30/2/356 |
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