E. V. Korneeva, O. V. Loseva, A. I. Smolentsev, A. V. Ivanov
{"title":"含有新型银(I)阴离子的双三维伪聚合物[Au{S2CN(CH2)6}2]4[Ag5Cl9]的合成、超分子自组织和热行为","authors":"E. V. Korneeva, O. V. Loseva, A. I. Smolentsev, A. V. Ivanov","doi":"10.1134/S1070328423600572","DOIUrl":null,"url":null,"abstract":"<p>New crystalline pseudo-polymer complex [Au{S<sub>2</sub>CN(CH<sub>2</sub>)<sub>6</sub>}<sub>2</sub>]<sub>4</sub>[Ag<sub>5</sub>Cl<sub>9</sub>] (<b>I</b>) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl<sub>3</sub>/2.5 M NaCl solution. Complex <b>I</b> was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [Au{S<sub>2</sub>CN(CH<sub>2</sub>)<sub>6</sub>}<sub>2</sub>]<sup>+</sup> (<i>A</i> : 2<i>B</i> : <i>C</i>) and complicated pentanuclear anion [Ag<sub>5</sub>Cl<sub>9</sub>]<sup>4–</sup> are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex <b>I</b> occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex <b>I</b> is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)–Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Double Three-Dimensional Pseudo-Polymer Complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] Comprising the New Type Silver(I) Anion\",\"authors\":\"E. V. Korneeva, O. V. Loseva, A. I. Smolentsev, A. V. Ivanov\",\"doi\":\"10.1134/S1070328423600572\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>New crystalline pseudo-polymer complex [Au{S<sub>2</sub>CN(CH<sub>2</sub>)<sub>6</sub>}<sub>2</sub>]<sub>4</sub>[Ag<sub>5</sub>Cl<sub>9</sub>] (<b>I</b>) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl<sub>3</sub>/2.5 M NaCl solution. Complex <b>I</b> was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [Au{S<sub>2</sub>CN(CH<sub>2</sub>)<sub>6</sub>}<sub>2</sub>]<sup>+</sup> (<i>A</i> : 2<i>B</i> : <i>C</i>) and complicated pentanuclear anion [Ag<sub>5</sub>Cl<sub>9</sub>]<sup>4–</sup> are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex <b>I</b> occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex <b>I</b> is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)–Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.</p>\",\"PeriodicalId\":1,\"journal\":{\"name\":\"Accounts of Chemical Research\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.4000,\"publicationDate\":\"2024-05-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Accounts of Chemical Research\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S1070328423600572\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Accounts of Chemical Research","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S1070328423600572","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
摘要 从 AuCl3/2.5 M NaCl 溶液中将金(III)与六亚甲基二硫代氨基甲酸银(I)结合,得到了新型结晶假聚合物络合物 [Au{S2CN(CH2)6}2]4[Ag5Cl9](I)。络合物 I 以制备的产量分离出来,并进行了结构表征。X 射线衍射 (XRD) 数据(CIF 文件 CCDC 编号:2205197)显示,[Au{S2CN(CH2)6}2]+(A : 2B : C)的异构阳离子和复杂的五核阴离子 [Ag5Cl9]4- 是该化合物的主要结构单元。由于 Cl--S、Ag--S、氢键 C--H--Cl、C--H--Ag 等多种次级相互作用,复合物 I 中的离子结构单元发生了超分子自组织,从而形成了三维伪聚合物框架。通过同步热分析研究了复合物 I 的热行为,发现在相对温和的条件下,双 Au(III)-Ag(I)化合物的热分解伴随着结合金属的定量再生。
Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Double Three-Dimensional Pseudo-Polymer Complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] Comprising the New Type Silver(I) Anion
New crystalline pseudo-polymer complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] (I) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [Au{S2CN(CH2)6}2]+ (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9]4– are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)–Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.
期刊介绍:
Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance.
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