Rakhi Nandy, Narayan Ch. Jana, Marko Jagodič, Zvonko Jagličić, Paula Brandão, Amrita Saha and Anangamohan Panja
{"title":"顺磁CuII和反磁nii离子对显示缓慢磁化弛豫的异双核3d-4f配合物单分子磁性的影响","authors":"Rakhi Nandy, Narayan Ch. Jana, Marko Jagodič, Zvonko Jagličić, Paula Brandão, Amrita Saha and Anangamohan Panja","doi":"10.1039/D4NJ04958F","DOIUrl":null,"url":null,"abstract":"<p >The fascinating field of 3d–4f single-molecule magnets (SMMs) has gained considerable attention since the breakthrough work of slow relaxation of magnetization in a Cu<small><sup>II</sup></small>–Tb<small><sup>III</sup></small> system. In this report, we present the synthesis of three new isostructural and isomorphous [CuLn(L)(NO<small><sub>3</sub></small>)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)] complexes (Ln = Gd (<strong>1</strong>), Tb (<strong>2</strong>), and Dy (<strong>3</strong>)), derived from a compartmental Schiff base ligand, H<small><sub>2</sub></small>L. To further unravel the magnetic dynamics, we also developed two closely related Zn<small><sup>II</sup></small>–Dy<small><sup>III</sup></small> complexes, [ZnDy(L)(NO<small><sub>3</sub></small>)<small><sub>3</sub></small>(py)] (<strong>4</strong>) and [ZnDy(L)(OAc)(piv)(NO<small><sub>3</sub></small>)] (<strong>5</strong>), with py, OAc, and piv representing pyridine, acetate, and pivalate ions, respectively. These complexes offer an opportunity to explore the influence of paramagnetic Cu<small><sup>II</sup></small> and diamagnetic Zn<small><sup>II</sup></small> ions on dynamic magnetic behaviors. Magnetic susceptibility measurements indicate a dominant Stark sublevel depopulation effect for the Dy<small><sup>III</sup></small> ions in complexes <strong>4</strong> and <strong>5</strong>, alongside pronounced ferromagnetic interactions between the Cu<small><sup>II</sup></small> ion and the respective Ln<small><sup>III</sup></small> ions in <strong>1–3</strong>, as commonly observed for ≥4f<small><sup>7</sup></small> ions. Intriguingly, all synthesized complexes exhibit dynamic magnetic behavior in the presence of an applied magnetic field, indicating that the ferromagnetic influence of Cu<small><sup>II</sup></small> ions and the charge polarization from the Zn<small><sup>II</sup></small> ion play crucial roles in shaping their magnetic properties. The most important achievement of this study is the observation of field-induced slow relaxation of magnetization in complex <strong>1</strong>, despite the isotropic nature of the Gd<small><sup>III</sup></small> ion. Given the scarcity of Cu<small><sup>II</sup></small>–Gd<small><sup>III</sup></small> systems demonstrating single-molecule magnet behavior, this work adds a remarkable contribution to the expanding field of Gd<small><sup>III</sup></small>-based SMMs, offering fresh insights and broadening the horizons of future research in this promising area.</p>","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":" 4","pages":" 1196-1207"},"PeriodicalIF":2.5000,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Impact of paramagnetic CuII and diamagnetic ZnII ions on single-molecule magnetism in heterodinuclear 3d–4f complexes displaying slow relaxation of magnetization†\",\"authors\":\"Rakhi Nandy, Narayan Ch. Jana, Marko Jagodič, Zvonko Jagličić, Paula Brandão, Amrita Saha and Anangamohan Panja\",\"doi\":\"10.1039/D4NJ04958F\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The fascinating field of 3d–4f single-molecule magnets (SMMs) has gained considerable attention since the breakthrough work of slow relaxation of magnetization in a Cu<small><sup>II</sup></small>–Tb<small><sup>III</sup></small> system. In this report, we present the synthesis of three new isostructural and isomorphous [CuLn(L)(NO<small><sub>3</sub></small>)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)] complexes (Ln = Gd (<strong>1</strong>), Tb (<strong>2</strong>), and Dy (<strong>3</strong>)), derived from a compartmental Schiff base ligand, H<small><sub>2</sub></small>L. To further unravel the magnetic dynamics, we also developed two closely related Zn<small><sup>II</sup></small>–Dy<small><sup>III</sup></small> complexes, [ZnDy(L)(NO<small><sub>3</sub></small>)<small><sub>3</sub></small>(py)] (<strong>4</strong>) and [ZnDy(L)(OAc)(piv)(NO<small><sub>3</sub></small>)] (<strong>5</strong>), with py, OAc, and piv representing pyridine, acetate, and pivalate ions, respectively. These complexes offer an opportunity to explore the influence of paramagnetic Cu<small><sup>II</sup></small> and diamagnetic Zn<small><sup>II</sup></small> ions on dynamic magnetic behaviors. Magnetic susceptibility measurements indicate a dominant Stark sublevel depopulation effect for the Dy<small><sup>III</sup></small> ions in complexes <strong>4</strong> and <strong>5</strong>, alongside pronounced ferromagnetic interactions between the Cu<small><sup>II</sup></small> ion and the respective Ln<small><sup>III</sup></small> ions in <strong>1–3</strong>, as commonly observed for ≥4f<small><sup>7</sup></small> ions. Intriguingly, all synthesized complexes exhibit dynamic magnetic behavior in the presence of an applied magnetic field, indicating that the ferromagnetic influence of Cu<small><sup>II</sup></small> ions and the charge polarization from the Zn<small><sup>II</sup></small> ion play crucial roles in shaping their magnetic properties. The most important achievement of this study is the observation of field-induced slow relaxation of magnetization in complex <strong>1</strong>, despite the isotropic nature of the Gd<small><sup>III</sup></small> ion. Given the scarcity of Cu<small><sup>II</sup></small>–Gd<small><sup>III</sup></small> systems demonstrating single-molecule magnet behavior, this work adds a remarkable contribution to the expanding field of Gd<small><sup>III</sup></small>-based SMMs, offering fresh insights and broadening the horizons of future research in this promising area.</p>\",\"PeriodicalId\":95,\"journal\":{\"name\":\"New Journal of Chemistry\",\"volume\":\" 4\",\"pages\":\" 1196-1207\"},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-12-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"New Journal of Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/nj/d4nj04958f\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"New Journal of Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/nj/d4nj04958f","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Impact of paramagnetic CuII and diamagnetic ZnII ions on single-molecule magnetism in heterodinuclear 3d–4f complexes displaying slow relaxation of magnetization†
The fascinating field of 3d–4f single-molecule magnets (SMMs) has gained considerable attention since the breakthrough work of slow relaxation of magnetization in a CuII–TbIII system. In this report, we present the synthesis of three new isostructural and isomorphous [CuLn(L)(NO3)3(H2O)] complexes (Ln = Gd (1), Tb (2), and Dy (3)), derived from a compartmental Schiff base ligand, H2L. To further unravel the magnetic dynamics, we also developed two closely related ZnII–DyIII complexes, [ZnDy(L)(NO3)3(py)] (4) and [ZnDy(L)(OAc)(piv)(NO3)] (5), with py, OAc, and piv representing pyridine, acetate, and pivalate ions, respectively. These complexes offer an opportunity to explore the influence of paramagnetic CuII and diamagnetic ZnII ions on dynamic magnetic behaviors. Magnetic susceptibility measurements indicate a dominant Stark sublevel depopulation effect for the DyIII ions in complexes 4 and 5, alongside pronounced ferromagnetic interactions between the CuII ion and the respective LnIII ions in 1–3, as commonly observed for ≥4f7 ions. Intriguingly, all synthesized complexes exhibit dynamic magnetic behavior in the presence of an applied magnetic field, indicating that the ferromagnetic influence of CuII ions and the charge polarization from the ZnII ion play crucial roles in shaping their magnetic properties. The most important achievement of this study is the observation of field-induced slow relaxation of magnetization in complex 1, despite the isotropic nature of the GdIII ion. Given the scarcity of CuII–GdIII systems demonstrating single-molecule magnet behavior, this work adds a remarkable contribution to the expanding field of GdIII-based SMMs, offering fresh insights and broadening the horizons of future research in this promising area.