{"title":"基于杂蝎酸配体的铁(II)复合物在室温下的渐变自旋交叉行为","authors":"Oleksandr Horniichuk, Laure Vendier, Lionel Salmon, Azzedine Bousseksou","doi":"10.1039/d4dt02244k","DOIUrl":null,"url":null,"abstract":"In this paper, we report the synthesis of six novel triazol-based heteroscorpionate ligands based on heterocycle metathesis reactions and their Iron(II) complexes. Single crystal structural analyses, spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex Bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior encompassing room temperature. The profile of the SCO curve can be explain by the presence of only relatively weak H-bondings spreading only in one dimension. Among the interesting spin transition behaviors observed for the different complexes, such stable, complete and gradual spin crossover at room temperature makes this neutral complex a good candidate for sublimation and future investigation as active element notably for thermoreflectance-based surface microthermometry applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Gradual spin crossover behavior encompassing room temperature in an Iron(II) complex based on heteroscorpionate ligand\",\"authors\":\"Oleksandr Horniichuk, Laure Vendier, Lionel Salmon, Azzedine Bousseksou\",\"doi\":\"10.1039/d4dt02244k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"In this paper, we report the synthesis of six novel triazol-based heteroscorpionate ligands based on heterocycle metathesis reactions and their Iron(II) complexes. Single crystal structural analyses, spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex Bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior encompassing room temperature. The profile of the SCO curve can be explain by the presence of only relatively weak H-bondings spreading only in one dimension. Among the interesting spin transition behaviors observed for the different complexes, such stable, complete and gradual spin crossover at room temperature makes this neutral complex a good candidate for sublimation and future investigation as active element notably for thermoreflectance-based surface microthermometry applications.\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2024-09-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4dt02244k\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4dt02244k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
本文报告了基于杂环偏合成反应合成的六种新型三唑基杂蝎酸盐配体及其铁(II)配合物。我们研究了所获配合物的单晶结构分析、光谱和磁性能,并将它们的自旋交叉结构关系与文献中报道的吡唑基类似物的自旋交叉结构关系进行了比较。特别是,在高压釜中氢气压力下,通过合成后催化硝基还原得到的氨基衍生物复合物双[氢双(吡唑-1-基)(3-氨基-1,2,4-三唑-1-基)]铁(II)在室温下呈现出稀少的渐变自旋交叉行为。SCO 曲线的剖面可以用仅在一个维度上存在相对较弱的 H 键来解释。在不同络合物中观察到的有趣的自旋转换行为中,室温下这种稳定、完全和渐进的自旋交叉使这种中性络合物成为升华和未来活性元素研究的理想候选物质,特别是在基于热反射的表面微测温应用中。
Gradual spin crossover behavior encompassing room temperature in an Iron(II) complex based on heteroscorpionate ligand
In this paper, we report the synthesis of six novel triazol-based heteroscorpionate ligands based on heterocycle metathesis reactions and their Iron(II) complexes. Single crystal structural analyses, spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex Bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior encompassing room temperature. The profile of the SCO curve can be explain by the presence of only relatively weak H-bondings spreading only in one dimension. Among the interesting spin transition behaviors observed for the different complexes, such stable, complete and gradual spin crossover at room temperature makes this neutral complex a good candidate for sublimation and future investigation as active element notably for thermoreflectance-based surface microthermometry applications.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.