{"title":"基于肼配体的一维和二维钠配位聚合物的无溶剂二氧化碳环化反应","authors":"","doi":"10.1016/j.jssc.2024.124973","DOIUrl":null,"url":null,"abstract":"<div><p>We successfully synthesized and characterized four new coordination polymers of sodium: sodium 4-hydroxy-3-{[2-(pyridine-4-carbonyl)hydrazinylidene]methyl}benzene-1-sulfonate (<strong>NaL</strong><sup><strong>4-Py</strong></sup>), sodium 3-[(2-benzoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (<strong>NaL</strong><sup><strong>Ph</strong></sup>), sodium 3-[(2-acetylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (<strong>NaL</strong><sup><strong>Me</strong></sup>), and sodium 3-[(2-carbamoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (<strong>NaL</strong><sup><strong>NH2</strong></sup>). These polymers were synthesized through a 1:1 condensation reaction of hydrazide derivatives with sodium salicylaldehyde-5-sulfonate monohydrate (NaSalSO<sub>3</sub>) and were thoroughly characterized using various analytical techniques. The compounds <strong>NaL</strong><sup><strong>Me</strong></sup> and <strong>NaL</strong><sup><strong>Ph</strong></sup>, crystallized in the P <span><math><mrow><mover><mn>1</mn><mo>‾</mo></mover></mrow></math></span> and P2<sub>1</sub>/n space groups, respectively, forming one-dimensional polymers. On the other hand, <strong>NaL</strong><sup><strong>NH2</strong></sup> and <strong>NaL</strong><sup><strong>4-Py</strong></sup> crystallized in the <em>Cmca</em> and P <span><math><mrow><mover><mn>1</mn><mo>‾</mo></mover></mrow></math></span> space groups, respectively, forming two-dimensional coordination polymers. The coordination environment of the sodium cation differed among the compounds, with the imine nitrogen atom interfering in <strong>NaL</strong><sup><strong>4-Py</strong></sup> and <strong>NaL</strong><sup><strong>Ph</strong></sup>. The sulfonate group exhibited various coordination modes, resulting in the different dimensionalities of the polymers. Compounds <strong>NaL</strong><sup><strong>4-Py</strong></sup> and <strong>NaL</strong><sup><strong>Ph</strong></sup> acted as heterogeneous Lewis acid catalysts for the solvent-free cycloaddition reaction of epichlorohydrine and CO<sub>2</sub> into valued cyclic carbonate. High selective conversion (68 %) of epichlorohydrin to cyclic carbonate was obtained at mild conditions, 60 °C and 1 bar CO<sub>2</sub>, after 24 h of reaction.</p></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Solvent-free CO2 cycloaddition by one- and two-dimensional sodium coordination polymers based on hydrazonic ligands\",\"authors\":\"\",\"doi\":\"10.1016/j.jssc.2024.124973\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>We successfully synthesized and characterized four new coordination polymers of sodium: sodium 4-hydroxy-3-{[2-(pyridine-4-carbonyl)hydrazinylidene]methyl}benzene-1-sulfonate (<strong>NaL</strong><sup><strong>4-Py</strong></sup>), sodium 3-[(2-benzoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (<strong>NaL</strong><sup><strong>Ph</strong></sup>), sodium 3-[(2-acetylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (<strong>NaL</strong><sup><strong>Me</strong></sup>), and sodium 3-[(2-carbamoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (<strong>NaL</strong><sup><strong>NH2</strong></sup>). These polymers were synthesized through a 1:1 condensation reaction of hydrazide derivatives with sodium salicylaldehyde-5-sulfonate monohydrate (NaSalSO<sub>3</sub>) and were thoroughly characterized using various analytical techniques. The compounds <strong>NaL</strong><sup><strong>Me</strong></sup> and <strong>NaL</strong><sup><strong>Ph</strong></sup>, crystallized in the P <span><math><mrow><mover><mn>1</mn><mo>‾</mo></mover></mrow></math></span> and P2<sub>1</sub>/n space groups, respectively, forming one-dimensional polymers. On the other hand, <strong>NaL</strong><sup><strong>NH2</strong></sup> and <strong>NaL</strong><sup><strong>4-Py</strong></sup> crystallized in the <em>Cmca</em> and P <span><math><mrow><mover><mn>1</mn><mo>‾</mo></mover></mrow></math></span> space groups, respectively, forming two-dimensional coordination polymers. The coordination environment of the sodium cation differed among the compounds, with the imine nitrogen atom interfering in <strong>NaL</strong><sup><strong>4-Py</strong></sup> and <strong>NaL</strong><sup><strong>Ph</strong></sup>. The sulfonate group exhibited various coordination modes, resulting in the different dimensionalities of the polymers. Compounds <strong>NaL</strong><sup><strong>4-Py</strong></sup> and <strong>NaL</strong><sup><strong>Ph</strong></sup> acted as heterogeneous Lewis acid catalysts for the solvent-free cycloaddition reaction of epichlorohydrine and CO<sub>2</sub> into valued cyclic carbonate. High selective conversion (68 %) of epichlorohydrin to cyclic carbonate was obtained at mild conditions, 60 °C and 1 bar CO<sub>2</sub>, after 24 h of reaction.</p></div>\",\"PeriodicalId\":378,\"journal\":{\"name\":\"Journal of Solid State Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2024-08-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Solid State Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022459624004274\",\"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":"Journal of Solid State Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022459624004274","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
我们成功合成并鉴定了四种新型钠配位聚合物:4-羟基-3-{[2-(吡啶-4-羰基)肼亚基]甲基}苯-1-磺酸钠(NaL4-Py)、3-[(2-苯甲酰基肼亚基)甲基]-4-羟基苯-1-磺酸钠(NaLPh)3-[(2-乙酰基肼亚基)甲基]-4-羟基苯-1-磺酸钠(NaLMe)和 3-[(2-氨基甲酰基肼亚基)甲基]-4-羟基苯-1-磺酸钠(NaLNH2)。这些聚合物是通过酰肼衍生物与水杨醛-5-磺酸钠一水合物(NaSalSO3)发生 1:1 缩合反应合成的,并利用各种分析技术对其进行了全面的表征。化合物 NaLMe 和 NaLPh 分别在 P 1‾ 和 P21/n 空间群中结晶,形成一维聚合物。另一方面,NaLNH2 和 NaL4-Py 分别在 Cmca 和 P 1‾ 空间群中结晶,形成二维配位聚合物。不同化合物中钠阳离子的配位环境各不相同,NaL4-Py 和 NaLPh 中的亚胺氮原子相互干扰,而磺酸基则表现出不同的配位模式,从而导致聚合物的尺寸不同。NaL4-Py 和 NaLPh 化合物可作为异相路易斯酸催化剂,用于环氧氯丙烷与 CO2 的无溶剂环加成反应,将其转化为有价环状碳酸盐。在 60 °C 和 1 bar CO2 的温和条件下,经过 24 小时的反应,环氧氯丙烷被高选择性地转化为环碳酸盐(68%)。
Solvent-free CO2 cycloaddition by one- and two-dimensional sodium coordination polymers based on hydrazonic ligands
We successfully synthesized and characterized four new coordination polymers of sodium: sodium 4-hydroxy-3-{[2-(pyridine-4-carbonyl)hydrazinylidene]methyl}benzene-1-sulfonate (NaL4-Py), sodium 3-[(2-benzoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLPh), sodium 3-[(2-acetylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLMe), and sodium 3-[(2-carbamoylhydrazinylidene)methyl]-4-hydroxybenzene-1-sulfonate (NaLNH2). These polymers were synthesized through a 1:1 condensation reaction of hydrazide derivatives with sodium salicylaldehyde-5-sulfonate monohydrate (NaSalSO3) and were thoroughly characterized using various analytical techniques. The compounds NaLMe and NaLPh, crystallized in the P and P21/n space groups, respectively, forming one-dimensional polymers. On the other hand, NaLNH2 and NaL4-Py crystallized in the Cmca and P space groups, respectively, forming two-dimensional coordination polymers. The coordination environment of the sodium cation differed among the compounds, with the imine nitrogen atom interfering in NaL4-Py and NaLPh. The sulfonate group exhibited various coordination modes, resulting in the different dimensionalities of the polymers. Compounds NaL4-Py and NaLPh acted as heterogeneous Lewis acid catalysts for the solvent-free cycloaddition reaction of epichlorohydrine and CO2 into valued cyclic carbonate. High selective conversion (68 %) of epichlorohydrin to cyclic carbonate was obtained at mild conditions, 60 °C and 1 bar CO2, after 24 h of reaction.
期刊介绍:
Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.