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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Encapsulation of [X_2(H_2O)_4]~(2-) (X = F/Cl) clusters by pyridyl terminated tripodal amide receptor in aqueous medium: single crystal X-ray structural evidence
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Encapsulation of [X_2(H_2O)_4]~(2-) (X = F/Cl) clusters by pyridyl terminated tripodal amide receptor in aqueous medium: single crystal X-ray structural evidence

机译:吡啶基封端的三足酰胺受体在水介质中包裹[X_2(H_2O)_4]〜(2-)(X = F / Cl)团簇:单晶X射线结构证据

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摘要

A new tris-amide receptor L based on 1,3,5-methyl substituted benzene platform and pyridyl as an attached unit is synthesized and explored towards anion recognition in aqueous environment. The presence of pyridyl terminal in L facilitates its aqueous solubility. The binding of halides and oxyanions towards L are examined by ~1H-NMR technique in solution and by single crystal X-ray crystallography in solid state studies. Crystallization of fluoride and chloride with L is carried out in acetone-water (1:1, v/v) binary solvent mixture that yields crystals for respective host-guest complexes, [L]_2?[F_2(H_2O)_4]?[TBA]_2 (1) and [L]_2?[Cl_2(H_2O)_4]?[TBA]_2 (2) suitable for single crystal X-ray diffraction studies. On the other hand, complexation of L with fluoride in dioxane-acetone (1:1, v/v) solvent mixture, results the formation of SiF_6 2-encapsulated complex, [L]_2?[SiF_6(H_2O)_2]?[TBA]_2 (3). Crystallographic result shows the formation of [F_2(H_2O)_4]_2- and [Cl_2(H_2O)_4]~(2-) zipped 1D-polymeric tweezer-like assemblies of L in acetone-water (1:1, v/v) binary solvent mixture in complexes 1 and 2 respectively. Solution state ~1H-NMR studies in D2O-acetone-d6 (1:19, v/v) support 1:4 (host-guest) binding stoichiometry of F~-, Cl~-, Br~-, NO_3~-, HSO_4~- and H_2PO_4~- with L. Binding constants of these investigated anions with L by 1:1 binding model are calculated which show the following binding order: NO_3~- ≈ HSO_4~- > F~- ≈ Cl~- ≈ Br~- > H_2PO_4~-. Further, solution state ~(19F-NMR studies are also carried out to establish the F~- binding with L in DMSO-d_6.
机译:合成了一种新的基于1,3,5-甲基取代苯平台和吡啶基为连接单元的三酰胺受体L,并探索了在水性环境中识别阴离子的方法。 L中吡啶基末端的存在促进了其水溶性。通过溶液中的〜1H-NMR技术和固态研究中的单晶X射线晶体学检查了卤化物和氧阴离子对L的结合。氟化物和氯化物与L的结晶是在丙酮-水(1:1,v / v)二元溶剂混合物中进行的,生成的每种主体-客体配合物[L] _2?[F_2(H_2O)_4]?[ TBA] _2(1)和[L] _2→[Cl_2(H_2O)_4]→[TBA] _2(2)适用于单晶X射线衍射研究。另一方面,L与氟化物在二恶烷-丙酮(1:1,v / v)溶剂混合物中的络合导致形成SiF_6 2包封的复合物[L] _2→[SiF_6(H_2O)_2]→[待定] _2(3)。晶体学结果表明,在丙酮-水(1:1,v / v)中形成了L的[F_2(H_2O)_4] _2-和[Cl_2(H_2O)_4]〜(2-)拉链状1D聚合物镊子状组装体。 )分别在配合物1和2中的二元溶剂混合物。在D2O-丙酮-d6(1:19,v / v)中的溶液状态〜1H-NMR研究支持F〜-,Cl〜-,Br〜-,NO_3〜-的1:4(客体)结合化学计量。 HSO_4〜-和H_2PO_4〜-与L的结合常数。计算这些被调查的阴离子与L的结合常数(通过1:1结合模型),显示出以下结合顺序:NO_3〜-≈HSO_4〜-> F〜-≈Cl〜-≈Br 〜-> H_2PO_4〜-。此外,还进行了溶液状态〜(19F-NMR研究,以建立与DMSO-d_6中的L的F〜-结合。

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