{"title":"热变色霍夫曼克拉斯衍生物中的电子转移诱导结构改性。","authors":"Livia Getzner, Yasmine Remili, Zakaria Ziani, Laure Vendier, Gábor Molnár, Saioa Cobo, Azzedine Bousseksou","doi":"10.1021/acs.inorgchem.4c04155","DOIUrl":null,"url":null,"abstract":"<p><p>This study explores a Hofmann-type clathrate, {Fe<sub>2</sub>(2,4-(OCH<sub>3</sub>)<sub>2</sub>-<i>p</i>bpy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[μ<sub>2</sub>-Pt(CN)<sub>4</sub>][μ<sub>3</sub>-Pt(CN)<sub>4</sub>]<sub>2</sub>·4H<sub>2</sub>O}, which exhibits a thermally activated electron transfer (ET) without spin crossover. Synthesized as microcrystalline powders and single crystals, this compound reveals significant structural changes upon variation of the temperature, including alterations in the iron coordination sphere due to the large movement of the bipyridinium ligand. These changes correlate with a thermochromic hysteretic transition from yellow to orange. Detailed characterizations using X-ray diffraction and IR spectroscopy indicate the involvement of nonbridging CN<sup>-</sup> moieties as electron donors and bipyridinium units as acceptors. This result deepens our understanding of ET in Hofmann-type clathrates.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3000,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electron-Transfer-Induced Structural Modification in a Thermochromic Hofmann Clathrate Derivative.\",\"authors\":\"Livia Getzner, Yasmine Remili, Zakaria Ziani, Laure Vendier, Gábor Molnár, Saioa Cobo, Azzedine Bousseksou\",\"doi\":\"10.1021/acs.inorgchem.4c04155\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>This study explores a Hofmann-type clathrate, {Fe<sub>2</sub>(2,4-(OCH<sub>3</sub>)<sub>2</sub>-<i>p</i>bpy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[μ<sub>2</sub>-Pt(CN)<sub>4</sub>][μ<sub>3</sub>-Pt(CN)<sub>4</sub>]<sub>2</sub>·4H<sub>2</sub>O}, which exhibits a thermally activated electron transfer (ET) without spin crossover. Synthesized as microcrystalline powders and single crystals, this compound reveals significant structural changes upon variation of the temperature, including alterations in the iron coordination sphere due to the large movement of the bipyridinium ligand. These changes correlate with a thermochromic hysteretic transition from yellow to orange. Detailed characterizations using X-ray diffraction and IR spectroscopy indicate the involvement of nonbridging CN<sup>-</sup> moieties as electron donors and bipyridinium units as acceptors. This result deepens our understanding of ET in Hofmann-type clathrates.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\" \",\"pages\":\"\"},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-11-28\",\"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.4c04155\",\"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.4c04155","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
本研究探讨了一种霍夫曼型克拉斯，即{Fe2(2,4-(OCH3)2-pbpy)2(H2O)2[μ2-Pt(CN)4][μ3-Pt(CN)4]2-4H2O}，它表现出一种热激活电子转移（ET）而无自旋交叉。这种化合物被合成为微晶粉末和单晶，在温度变化时会出现显著的结构变化，包括由于联吡啶配体的大幅移动而导致铁配位层的变化。这些变化与从黄色到橙色的热致变色转变有关。利用 X 射线衍射和红外光谱进行的详细表征表明，非杂化 CN- 分子是电子供体，而双吡啶鎓单元是受体。这一结果加深了我们对霍夫曼型氯化物中 ET 的理解。
Electron-Transfer-Induced Structural Modification in a Thermochromic Hofmann Clathrate Derivative.
This study explores a Hofmann-type clathrate, {Fe2(2,4-(OCH3)2-pbpy)2(H2O)2[μ2-Pt(CN)4][μ3-Pt(CN)4]2·4H2O}, which exhibits a thermally activated electron transfer (ET) without spin crossover. Synthesized as microcrystalline powders and single crystals, this compound reveals significant structural changes upon variation of the temperature, including alterations in the iron coordination sphere due to the large movement of the bipyridinium ligand. These changes correlate with a thermochromic hysteretic transition from yellow to orange. Detailed characterizations using X-ray diffraction and IR spectroscopy indicate the involvement of nonbridging CN- moieties as electron donors and bipyridinium units as acceptors. This result deepens our understanding of ET in Hofmann-type clathrates.
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.
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