【作者】 任海仙；

【导师】 张有明； 魏太保；

【作者基本信息】 西北师范大学 ， 无机化学， 2007， 硕士

【摘要】 分子识别是指主体对客体选择性结合并产生特定功能的过程,是超分子化学研究的重要内容。阴离子识别作为它的一个重要分支,近年来引起了国内外专家学者的广泛关注,其关键是合成具有高选择性的人工识别受体。本文合成了一系列新型的受体分子并研究了其阴离子识别性能,具体内容包括以下几部分:1.简要介绍阴离子识别的发展现状,并从以下几个方面进行剖析:（ⅰ）阴离子识别研究中所涉及的分子间相互作用力（ⅱ）阴离子识别的方法（ⅲ）阴离子受体的设计原则。2.合成了3种4′-乙酰基苯并-15-冠-5缩氨基硫脲衍生物受体分子,对其进行了表征。利用紫外-可见吸收光谱（UV-vis,DMSO为溶剂）考察了其与F、Cl^-、Br^-、I^-、CH₃COO^-、HSO₄^-和NO₃^-等阴离子的作用。结果表明,该类受体分子可与阴离子F^-、CH₃COO^-形成氢键配合物,从而实现对这两种阴离子的检测。通过计算可知,同种受体分子对此两种阴离子的作用为F^-＜CH₃COO^-。随着苯环上取代基位置的变化,此三种受体分子对两种阴离子的作用呈现出有规律的变化。3.本文设计合成了5种间苯二甲醛缩双芳氨基硫脲受体分子,利用紫外-可见吸收光谱及¹H NMR,考察了其与F^-、Cl^-、Br^-、I^-、CH₃COO^-、HSO₄^-、NO₃^-和H₂PO₄^-等8种阴离子的作用。当在受体分子的DMSO溶液中加入F^-和CH₃COO^-四丁基铵盐的DMSO溶液时,吸收光谱发生显著红移,溶液颜色立刻由无色转变为深黄色,而加入其它阴离子则无显著变化,从而可以实现对这2种阴离子的裸眼检测及光谱分析。通过计算可知,随着苯环上取代基的变化,此5种受体分子对F^-和CH₃COO^-的识别作用呈现有规律的变化。¹H NMR滴定及质子溶剂效应进一步证明了受体分子与阴离子之间以氢键作用方式相结合。Job工作曲线表明该类受体分子与阴离子形成配位比为1∶1的氢键配合物。4.设计合成了一种新型化合物1∶1,1′-（2,5-噻二唑-二硫乙酰基）4,4′-（对氯苯甲酰基）氨基硫脲,并用紫外光谱研究了其对阴离子客体的识别性能。主体1加入到对硝基酚氧阴离子（p-NO₂C₆H₄O^-）的DMSO溶液中,主客体间形成超分子配合物使得客体阴离子425nm处吸光度降低且溶液从黄色变为无色。受体1与F^-、CH₃COO^-和H₂PO₄^-相互作用,吸收光谱也发生一定变化,而与Cl^-、Br^-、I^-、HSO₄^-和NO₃^-作用,吸收光谱几乎没有变化。其吸收光谱改变强弱顺序为p-NO₂C₆H₄O＞F＞CH₃COO^-＞H₂PO₄^->>Cl^-、Br^-、I^-、HSO₄^-和NO₃^-。紫外光谱滴定的结果经非线性拟合,表明主客体间形成1∶1络合物,并且计算出受体与阴离子结合的稳定常数。质子溶剂效应进一步证明了受体分子与阴离子之间以氢键作用方式相结合。基于实验结果,对主客体之间的作用机理及识别模式作了初步探讨。5.设计合成了3种酰腙类受体分子。利用紫外-可见吸收光谱及¹H NMR考察了其与F^-、Cl^-、Br^-、I^-、CH₃COO^-、HSO₄^-、NO₃^-等阴离子的作用。结果表明,该类受体分子与阴离子形成氢键配合物。尤其对于受体3（间苯双对硝基苯氧乙酰腙）,加入F^-和CH₃COO^-时,溶液颜色有明显变化。更多还原

【Abstract】 Molecular recognition is the process that host molecular form binding with guest molecular selectively and produce some special function,which is an important research area in supramolecular chemistry.The anion recognition,as an important part of molecular recognition,has been given great attention from many specialists. We have synthesized some novel receptors and studied on their anion recognition properties.The major contents are as follows:1.Researches in the development of anion recognition were briefly reviewed on the following three sides:（ⅰ）Noncovalent interactions existed in anion coordination.（ⅱ） measure of anion recognition.（ⅲ）Design of anion receptors.2.A new series of receptors were designed and synthesized and their interactions with anions such as F^-,Cl^-,Br^-,I^-,CH₃COO^-,HSO₄^- and NO₃^- in DMSO solvent were investigated by using UV-Vis absorption spectroscopy.The results showed that the hydrogen-bonding complexes were formed between receptors and the tested anions such as CH₃COO^- and F.It was also found that the selectivity of receptors for anions could be efficiently tuned by changing the place of the substituent group at the N-phenyl moiety.The recognition mechanism and binding mode were discussed.3.Five new isophthalic aldehyde bisarylthiosemicarbazone receptors were designed and synthesized.The binding properties of the receptors with anions such as F^-,Cl^-,Br^-, I^-,CH₃COO^-,HSO₄^- and NO₃^- in DMSO were investigated by UV-Vis and ¹H NMR spectroscopy.A clear color change was observed from colorless to deep yellow upon addition of F^- and CH₃COO^- to the solution of the five receptors in DMSO.The results showed that the five receptors had a better selectivity of F^- and CH₃COO^-,but had no evident binding withCl^-,Br^-,I^-,HSO₄^- and NO₃^-.It was regular that the five receptors had different binding ability with F^- and CH₃COO^-.The UV-Vis data indicated that a 1:1 stoichiometry complex was formed between the receptors and the two anions.¹H NMR titrations and solvation effect confirmed hydrogen bonding interaction between the receptors and anions.4.A new thiosemicarbazide receptor 1:1,1’ -（2,5-thiadiazole-dithioaceto）4,4’ -（p-chlorine benzoyl）thiosemicarbazide was designed and synthesized.The binding properties of the receptor with anions such as F^-,Cl^-,Br^-,I^-,CH₃COO^-,HSO₄^-, NO₃^- and p-NO₂C₆H₄O^- and NO₃^- in DMSO were investigated by UV-Vis spectroscopy.Addition of host 1 to the p-NO₂C₆H₄O^- anion in DMSO resulted in decreasing absorption band at 425nm and the yellow solution of p-NO₂C₆H₄O^- anion became colorless because of the formation of host-guest complex between host 1 and p-NO₂C₆H₄O^-.The absorption spectra response was also observed in the presence of anions such as F^-,CH₃COO^- and H₂PO₄^-.The degree of change in the absorption spectra was in the order of p-NO₂C₆H₄O^-＞F^-＞CH3COO^-＞H₂PO₄^->>Cl^-,Br^-,I^-, HSO₄^-,NO₃^-.The UV-Vis spectroscopy titration experiments indicated the formation of a 1:1 stoichiometry complex between receptor 1 and anions by nonlinear curve fitting,as a result,the association constants were evaluated.Solvation effect confirmed hydrogen bonding interaction between the receptor and anions.Based on the above results,the recognition mechanism and binding mode were discussed.5.The synthesis and UV-vis and ¹H NMR spectroscopic studies of aryloxyacetyl hydrazide colorimetric sensors for anions are presented.These sensors can recognize anions through hydrogen binding even in competitive DMSO solutions,especially, the receptor 3（1,3-benzyldi（p-nitro-methylphenyloxy）acetylhydrozone）gives rise to large color change that are clearly visible to the naked eye.更多还原