Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide Biradical

The reaction of nitronyl nitroxide biradical NITPhMeImbis(5-(2-methylimidazole)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1<i>H</i>-imidazol-2-yl)-benzene) with Dy(hfac)<sub>3</sub> and La(hfac)<sub>3</sub> (hfac = hexafluoroacetylacetonate) affor...

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Main Authors: Yan Zhou, Junfang Xie, Chaoyi Jin, Yue Ma, Licun Li
Format: Article
Language:English
Published: MDPI AG 2025-03-01
Series:Magnetochemistry
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Online Access:https://www.mdpi.com/2312-7481/11/4/26
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author Yan Zhou
Junfang Xie
Chaoyi Jin
Yue Ma
Licun Li
author_facet Yan Zhou
Junfang Xie
Chaoyi Jin
Yue Ma
Licun Li
author_sort Yan Zhou
collection DOAJ
description The reaction of nitronyl nitroxide biradical NITPhMeImbis(5-(2-methylimidazole)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1<i>H</i>-imidazol-2-yl)-benzene) with Dy(hfac)<sub>3</sub> and La(hfac)<sub>3</sub> (hfac = hexafluoroacetylacetonate) afforded a heterolanthanide complex [Dy<sub>0.56</sub>La<sub>1.44</sub>(hfac)<sub>7</sub>(NITPhMeImbisH)] (<b>1</b>). In this complex, the biradical NITPhMeImbis ligand chelates one Ln(III) ion via its two neighboring NO units and simultaneously binds the La(III) ion through another NO group to form a dinuclear structure. Direct current (dc) magnetic measurement shows the dominant ferromagnetic couplings in Complex <b>1</b>. Spin dynamics studies exhibit visible frequency-dependent peaks of <i>χ</i>″ signals under a dc field evidenced by field-induced magnetic relaxation behavior, which is a combination of Orbach and QTM processes, giving the <i>U</i><sub>eff</sub>, <i>τ</i><sub>0</sub> and <i>τ</i><sub>QTM</sub> values of 15.14 K, 3.04 × 10<sup>−7</sup> s and 3.61 × 10<sup>−4</sup> s, respectively.
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publishDate 2025-03-01
publisher MDPI AG
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series Magnetochemistry
spelling doaj-art-6187eacb781b4f0ca80ea41e73b0f83c2025-08-20T02:18:09ZengMDPI AGMagnetochemistry2312-74812025-03-011142610.3390/magnetochemistry11040026Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide BiradicalYan Zhou0Junfang Xie1Chaoyi Jin2Yue Ma3Licun Li4Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry, College of Chemistry, Nankai University, Tianjin 300071, ChinaDepartment of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry, College of Chemistry, Nankai University, Tianjin 300071, ChinaDepartment of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry, College of Chemistry, Nankai University, Tianjin 300071, ChinaDepartment of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry, College of Chemistry, Nankai University, Tianjin 300071, ChinaDepartment of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry, College of Chemistry, Nankai University, Tianjin 300071, ChinaThe reaction of nitronyl nitroxide biradical NITPhMeImbis(5-(2-methylimidazole)-1,3-bis(1′-oxyl-3′-oxido-4′,4′,5′,5′-tetramethyl-4,5-hydro-1<i>H</i>-imidazol-2-yl)-benzene) with Dy(hfac)<sub>3</sub> and La(hfac)<sub>3</sub> (hfac = hexafluoroacetylacetonate) afforded a heterolanthanide complex [Dy<sub>0.56</sub>La<sub>1.44</sub>(hfac)<sub>7</sub>(NITPhMeImbisH)] (<b>1</b>). In this complex, the biradical NITPhMeImbis ligand chelates one Ln(III) ion via its two neighboring NO units and simultaneously binds the La(III) ion through another NO group to form a dinuclear structure. Direct current (dc) magnetic measurement shows the dominant ferromagnetic couplings in Complex <b>1</b>. Spin dynamics studies exhibit visible frequency-dependent peaks of <i>χ</i>″ signals under a dc field evidenced by field-induced magnetic relaxation behavior, which is a combination of Orbach and QTM processes, giving the <i>U</i><sub>eff</sub>, <i>τ</i><sub>0</sub> and <i>τ</i><sub>QTM</sub> values of 15.14 K, 3.04 × 10<sup>−7</sup> s and 3.61 × 10<sup>−4</sup> s, respectively.https://www.mdpi.com/2312-7481/11/4/26nitronyl nitroxide biradicalheterolanthanidecrystal structuremagnetic relaxation
spellingShingle Yan Zhou
Junfang Xie
Chaoyi Jin
Yue Ma
Licun Li
Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide Biradical
Magnetochemistry
nitronyl nitroxide biradical
heterolanthanide
crystal structure
magnetic relaxation
title Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide Biradical
title_full Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide Biradical
title_fullStr Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide Biradical
title_full_unstemmed Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide Biradical
title_short Magnetic Relaxation in a Heterolanthanide Binuclear Complex Involving a Nitronyl Nitroxide Biradical
title_sort magnetic relaxation in a heterolanthanide binuclear complex involving a nitronyl nitroxide biradical
topic nitronyl nitroxide biradical
heterolanthanide
crystal structure
magnetic relaxation
url https://www.mdpi.com/2312-7481/11/4/26
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AT chaoyijin magneticrelaxationinaheterolanthanidebinuclearcomplexinvolvinganitronylnitroxidebiradical
AT yuema magneticrelaxationinaheterolanthanidebinuclearcomplexinvolvinganitronylnitroxidebiradical
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