Svetlana V. Klementyeva, Michael T. Gamer, Michael Schulze, Nithin Suryadevara, Artem S. Bogomyakov, Pavel A. Abramov, Sergey N. Konchenko, Mario Ruben, Wolfgang Wernsdorfer, Eufemio Moreno-Pineda
{"title":"具有桥接3,5-二叔丁基儿茶酚酸酯的双核稀土β-二酮酸盐:合成、结构和单分子磁性","authors":"Svetlana V. Klementyeva, Michael T. Gamer, Michael Schulze, Nithin Suryadevara, Artem S. Bogomyakov, Pavel A. Abramov, Sergey N. Konchenko, Mario Ruben, Wolfgang Wernsdorfer, Eufemio Moreno-Pineda","doi":"10.1021/acs.inorgchem.4c03278","DOIUrl":null,"url":null,"abstract":"The dinuclear β-diketiminato complex [L<sup>1</sup>ClDy(μ-Cl)<sub>3</sub>DyL<sup>1</sup>(THF)] (<b>1</b>) (L<sup>1</sup> = {2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>–NC(Me)CHC(Me)N-2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}<sup>−</sup>) was obtained by reaction of DyCl<sub>3</sub> with KL<sup>1</sup> in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [L<sup>1</sup>Dy(μ-3,5-Cat)]<sub>2</sub> (<b>2</b>) by salt metathesis reaction with 3,5-CatK<sub>2</sub> (3,5-Cat −3,5-di-<i>tert</i>-butyl-catecholate). Reactions of 3,5-CatNa<sub>2</sub> with [L<sup>2</sup>LnCl<sub>2</sub>(THF)<sub>2</sub>] (Ln<sup>3+</sup> = Dy, Y) ligated with the less bulky ligand L<sup>2</sup> = {2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>–NC(Me)CHC(Me)N-2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>}<sup>−</sup> afforded the mixed-ligand THF-containing complexes [L<sup>2</sup>Ln(μ-3,5-Cat)(THF)]<sub>2</sub> (Ln<sup>3+</sup> = Dy (<b>3a</b>), Y (<b>3b</b>)). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction. Magnetic measurements revealed single-molecule magnet behavior for the dysprosium complexes. Sub-Kelvin μSQUID studies confirm the SMM character of the systems, while CASSCF calculation along with simulation of the experimental data yields an antiferromagnetic interaction operating between the Dy<sup>3+</sup> ions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.3000,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Ditert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties\",\"authors\":\"Svetlana V. Klementyeva, Michael T. Gamer, Michael Schulze, Nithin Suryadevara, Artem S. Bogomyakov, Pavel A. Abramov, Sergey N. Konchenko, Mario Ruben, Wolfgang Wernsdorfer, Eufemio Moreno-Pineda\",\"doi\":\"10.1021/acs.inorgchem.4c03278\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The dinuclear β-diketiminato complex [L<sup>1</sup>ClDy(μ-Cl)<sub>3</sub>DyL<sup>1</sup>(THF)] (<b>1</b>) (L<sup>1</sup> = {2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>–NC(Me)CHC(Me)N-2,6-<sup>i</sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}<sup>−</sup>) was obtained by reaction of DyCl<sub>3</sub> with KL<sup>1</sup> in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [L<sup>1</sup>Dy(μ-3,5-Cat)]<sub>2</sub> (<b>2</b>) by salt metathesis reaction with 3,5-CatK<sub>2</sub> (3,5-Cat −3,5-di-<i>tert</i>-butyl-catecholate). Reactions of 3,5-CatNa<sub>2</sub> with [L<sup>2</sup>LnCl<sub>2</sub>(THF)<sub>2</sub>] (Ln<sup>3+</sup> = Dy, Y) ligated with the less bulky ligand L<sup>2</sup> = {2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>–NC(Me)CHC(Me)N-2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>}<sup>−</sup> afforded the mixed-ligand THF-containing complexes [L<sup>2</sup>Ln(μ-3,5-Cat)(THF)]<sub>2</sub> (Ln<sup>3+</sup> = Dy (<b>3a</b>), Y (<b>3b</b>)). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction. Magnetic measurements revealed single-molecule magnet behavior for the dysprosium complexes. Sub-Kelvin μSQUID studies confirm the SMM character of the systems, while CASSCF calculation along with simulation of the experimental data yields an antiferromagnetic interaction operating between the Dy<sup>3+</sup> ions.\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"44 1\",\"pages\":\"\"},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-12-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.4c03278\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.4c03278","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
由DyCl3与KL1以1:1的摩尔比反应得到双核β-二酮酸配合物[L1ClDy(μ-Cl)3DyL1(THF)] (1) (L1 = {2,6- ipr2c6h3 - nc (Me)CHC(Me) n -2,6- ipr2c6h3}−),并与3,5- catk2 (3,5- cat−3,5-二叔丁基儿茶酚酸盐)进行盐还原反应制备混合配体配合物[L1Dy(μ-3,5- cat)]2(2)。与体积较小的配体L2 = {2,4,6- me3c6h2 - nc (Me)CHC(Me) n -2,4,6- me3c6h2}−结合的3,5- catna2与[L2Ln(μ-3,5- cat)(THF)]2 (Ln3+ = Dy (3a), Y (3b))反应得到混合配体含THF配合物[L2Ln(μ-3,5- cat)]2 (Ln3+ = Dy (3a), Y (3b))。所有新的配合物都被充分表征,并通过单晶x射线衍射确定了固体结构。磁性测量揭示了镝配合物的单分子磁性行为。亚开尔文μSQUID研究证实了系统的SMM特性,而CASSCF计算和实验数据的模拟得到了Dy3+离子之间的反铁磁相互作用。
Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Ditert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties
The dinuclear β-diketiminato complex [L1ClDy(μ-Cl)3DyL1(THF)] (1) (L1 = {2,6-iPr2C6H3–NC(Me)CHC(Me)N-2,6-iPr2C6H3}−) was obtained by reaction of DyCl3 with KL1 in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [L1Dy(μ-3,5-Cat)]2 (2) by salt metathesis reaction with 3,5-CatK2 (3,5-Cat −3,5-di-tert-butyl-catecholate). Reactions of 3,5-CatNa2 with [L2LnCl2(THF)2] (Ln3+ = Dy, Y) ligated with the less bulky ligand L2 = {2,4,6-Me3C6H2–NC(Me)CHC(Me)N-2,4,6-Me3C6H2}− afforded the mixed-ligand THF-containing complexes [L2Ln(μ-3,5-Cat)(THF)]2 (Ln3+ = Dy (3a), Y (3b)). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction. Magnetic measurements revealed single-molecule magnet behavior for the dysprosium complexes. Sub-Kelvin μSQUID studies confirm the SMM character of the systems, while CASSCF calculation along with simulation of the experimental data yields an antiferromagnetic interaction operating between the Dy3+ ions.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.