Narayan Ch. Jana, Albert Escuer, Radovan Herchel, Joan Serra, Rakhi Nandy, Anangamohan Panja
{"title":"Impact of 3d Metal Ions on the Magnetic Dynamics in Isostructural Tetranuclear Butterfly {Ni2IIDy2III} and {Co2IIDy2III} Complexes","authors":"Narayan Ch. Jana, Albert Escuer, Radovan Herchel, Joan Serra, Rakhi Nandy, Anangamohan Panja","doi":"10.1021/acs.cgd.4c00812","DOIUrl":null,"url":null,"abstract":"This paper describes the synthesis, structures, and magnetic properties of four isostructural butterfly-type heterometallic tetranuclear 3d-4f complexes, [Ni<sub>2</sub>Dy<sub>2</sub>(HL<sup>1</sup>)<sub>2</sub>(μ<sub>3</sub>–OH)<sub>2</sub>(piv)<sub>6</sub>]·2CH<sub>3</sub>CN (<b>1</b>), [Ni<sub>2</sub>Dy<sub>2</sub>(HL<sup>2</sup>)<sub>2</sub>(μ<sub>3</sub>–OH)<sub>2</sub>(piv)<sub>6</sub>]·2CH<sub>3</sub>CN (<b>2</b>), [Co<sub>2</sub>Dy<sub>2</sub>(HL<sup>1</sup>)<sub>2</sub>(μ<sub>3</sub>–OH)<sub>2</sub>(piv)<sub>6</sub>]·2H<sub>2</sub>O (<b>3</b>), and [Co<sub>2</sub>Dy<sub>2</sub>(HL<sup>2</sup>)<sub>2</sub>(μ<sub>3</sub>–OH)<sub>2</sub>(piv)<sub>6</sub>]·2CH<sub>3</sub>CN (<b>4</b>), derived from two closely related Schiff base ligands H<sub>2</sub>L<sup>1</sup> and H<sub>2</sub>L<sup>2</sup> in the presence of pivalate (piv) ions. X-ray crystallographic studies of <b>1</b>–<b>4</b> revealed that all of the complexes are constructed with a type-II butterfly core in which Dy<sup>III</sup> ions are located at body positions, while the 3d metal ions (Ni<sup>II</sup> and Co<sup>II</sup>) occupy the wingtip positions. It is noteworthy that all reported systems containing Ni<sup>II</sup> and Co<sup>II</sup> have been isolated as type-I butterfly structures, with only one report each on the Ni<sub>2</sub><sup>II</sup>Dy<sub>2</sub><sup>III</sup> and Co<sub>2</sub><sup>II</sup>Dy<sub>2</sub><sup>III</sup> type-II butterfly core systems, which have been both structurally and magnetically characterized. Direct current magnetic susceptibility measurements performed on <b>1</b>–<b>4</b> revealed that the susceptibility response is dominated by the depopulation of Stark sublevels of the Dy<sup>III</sup> ions and the ZFS of the Co<sup>II</sup> cations in the case of <b>3</b> and <b>4</b> and the weak intramolecular superexchange interactions have been calculated by means of CASSCF and CASSCF/NEVPT2 calculations. Dynamic magnetic studies revealed that only Co<sup>II</sup> analogues (<b>3</b> and <b>4</b>) display single-molecule magnet behaviors in which the additional anisotropy of the Co<sup>II</sup> centers is responsible for the occurrence of the out-of-phase response in contrast to <b>1</b> and <b>2</b> with poorly anisotropic Ni<sup>II</sup> cations.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Crystal Growth & Design","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.cgd.4c00812","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
This paper describes the synthesis, structures, and magnetic properties of four isostructural butterfly-type heterometallic tetranuclear 3d-4f complexes, [Ni2Dy2(HL1)2(μ3–OH)2(piv)6]·2CH3CN (1), [Ni2Dy2(HL2)2(μ3–OH)2(piv)6]·2CH3CN (2), [Co2Dy2(HL1)2(μ3–OH)2(piv)6]·2H2O (3), and [Co2Dy2(HL2)2(μ3–OH)2(piv)6]·2CH3CN (4), derived from two closely related Schiff base ligands H2L1 and H2L2 in the presence of pivalate (piv) ions. X-ray crystallographic studies of 1–4 revealed that all of the complexes are constructed with a type-II butterfly core in which DyIII ions are located at body positions, while the 3d metal ions (NiII and CoII) occupy the wingtip positions. It is noteworthy that all reported systems containing NiII and CoII have been isolated as type-I butterfly structures, with only one report each on the Ni2IIDy2III and Co2IIDy2III type-II butterfly core systems, which have been both structurally and magnetically characterized. Direct current magnetic susceptibility measurements performed on 1–4 revealed that the susceptibility response is dominated by the depopulation of Stark sublevels of the DyIII ions and the ZFS of the CoII cations in the case of 3 and 4 and the weak intramolecular superexchange interactions have been calculated by means of CASSCF and CASSCF/NEVPT2 calculations. Dynamic magnetic studies revealed that only CoII analogues (3 and 4) display single-molecule magnet behaviors in which the additional anisotropy of the CoII centers is responsible for the occurrence of the out-of-phase response in contrast to 1 and 2 with poorly anisotropic NiII cations.
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The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.
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