(硫)脲基萼片[4]炔衍生物在乙腈中与阴离子结合的热力学研究

IF 3.7 Q2 CHEMISTRY, PHYSICAL
Marija Cvetnić, Nikola Cindro, Nikola Bregović* and Vladislav Tomišić, 
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引用次数: 0

摘要

在这项工作中,我们开发了(硫)脲基萼[4]炔衍生物,并深入探讨了它们在乙腈中的阴离子结合特性。我们研究了一系列阴离子,包括重要的无机阴离子(Cl-、HSO4-、H2PO4- 和 HP2O73-)和几种常见的羧酸盐(醋酸盐、苯甲酸盐和富马酸盐)。所有系统都通过多种方法(核磁共振、ITC 和紫外线)进行了协同研究,从而提供了全面的热力学描述。受体的酸度是在阴离子结合研究之前确定的,并在数据处理程序中予以考虑。研究人员检测到了不同化学计量的络合物,并阐明了其形成的驱动力。阴离子结构特征和氢键受体特性与化学计量学和络合热力学参数的相关性也得到了合理的解释。一般来说,络合物的稳定性遵循阴离子碱性所确定的趋势。除了 H2PO4- 和 HP2O73- 与硫脲类似物的相互作用更强之外,硫脲和脲类似物在阴离子结合方面表现出相似的亲和力。具有 4 个(硫)脲基团的宿主形成了包含两个受体分子的物种,这两个受体分子由富马酸阴离子或焦磷酸氢阴离子桥接。这项工作提供的热力学信息适用于超分子系统的进一步设计,而提出的数据处理方法将有助于研究人员处理多种共存平衡。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Thermodynamics of Anion Binding by (Thio)ureido-calix[4]arene Derivatives in Acetonitrile

In this work, we developed (thio)ureido-calix[4]arene derivatives and thoroughly explored their anion-binding properties in acetonitrile. A series of anions, including important inorganic ones (Cl, HSO4, H2PO4, and HP2O73–) and several ever-present carboxylates (acetate, benzoate, and fumarate), were studied. All systems were investigated by several methods (NMR, ITC, and UV) used in a synergistic fashion, providing their comprehensive thermodynamic description. Acidities of the receptors were determined prior to the anion-binding studies and considered in the data-handling procedures. Complexes of various stoichiometries were detected and the driving force for their formation elucidated. The correlation of the anion structural features and H-bond acceptor properties with the stoichiometries and complexation thermodynamics parameters was rationalized. Generally, stability of the complexes followed the trend defined by the basicity of anions. Thiourea and urea analogues exhibited similar affinities for anion binding except for the H2PO4 and HP2O73–, which interacted with the thiourea analogue more strongly. The hosts endowed with 4 (thio)urea groups formed species containing two receptor molecules bridged by a fumarate or hydrogen pyrophosphate anion. Thermodynamic information provided in this work is applicable in further design of supramolecular systems, whereas the presented approach to data handling will aid researchers when dealing with multiple coexisting equilibria.

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来源期刊
CiteScore
3.70
自引率
0.00%
发文量
0
期刊介绍: ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis
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