【作者】 石雅琳；

【导师】 周稚仙； 吴养洁；

【作者基本信息】 郑州大学 ， 有机化学， 2002， 硕士

【摘要】 本论文设计、合成并表征了10种在杯芳烃下沿带有间位烷氧基羰基或羧基苄基的杯[4]芳烃衍生物，研究了它们与季铵盐正离子的包合性能和选择性，以及对中性有机分子的包合作用；研究了它们对稀土金属Tb³⁺的敏化发光性能。取得了以下结果： 一、设计合成了10种杯[4]芳烃衍生物，均经元素分析、红外光谱、核磁共振波谱鉴定，并确定了它们的构象。 二、通过差热—热重分析、X—射线粉末衍射对化合物4与四丁基溴化铵（TBAB）所形成的包合物（1:1）进行了表征，研究了4对季铵盐正离子的包合性能和选择性，证明了4确实能和四丁基溴化铵形成包合物；以4为载体制得的PVC膜离子选择电极的研究亦表明该电极对四丁基铵 正离子BWN”有很好的响应性能和选择性，从而为4包合Bll4N”提供了一 个可靠的佐证。三、研究了化合物4－13对稀土金属Tb’”的敏化发光性能并同邻位梭基或烷 氧基苦基取代的杯芳烃衍生物1447进行了比较。结果表明芋基上含梭 基门，12，13)的杯k］芳烃系列配体对 Tb’”的敏化效果良好，这可能 是由于侧链苯甲酸和骨架中苯环吸收的能量均能有效地传递给 Tb’“；而 间位梭基书基取代的化合物门，12)又比相应的邻位取代的衍生物门， 16)的敏化效果好。敏化发光效率可能与与配体的空间位阻以及形成的 配合物的稳定性有关。 r卜y卜 14 15 16 I7四、测定了化合物4、5、9和中性有机分子CH。CN、CH。NO。所形成的包合 物 L／CH。CN、L丫CH。NO。、L／CH；CN、L／CH3NO。以及化合物 10的晶 体结构。研究结果表明，含CH基团的中性有机分子不仅可以和具有C。 对称的主体分子（L。、L＊而且还可以和 C。对称的杯H芳烃衍生物①） 形成稳定的包合物；主体分子4。5、9依靠CH－。作用和客体分子形成 稳定的分子内包合物，但包合作用的强弱与客体的酸性无必然联系，而 和主、客体分子的空间结构有关。杯k］芳烃衍生物10的晶体结构表明， 10的每个分子的一个取代基中的乙基有序地进入到另一个分于的杯空腔 中，经测定，乙基中的甲基与另一个分子中杯卜］芳烃骨架苯环亦存在有 CH－。作用，这种自包结作用使该化合物在空间呈特殊的有规则的排列。更多还原

【Abstract】 In this thesis, ten novel calix[4]arene derivatives have been designed and synthesized, in which m-(alkoxycarbonyl)benzyl or w-(carboxy)benzyl are substituted on the lower rim of the calix[4]arenes. The inclusion behavior of the these calix[4]arene derivatives with tetrabutyl ammonium cation and neutral organic molecules has been studied. In addition, the sensitizing luminesence of Tb3+ by them was also studied. The main results obtained are as follows.1. Ten novel calix[4]arene derivateves were designed and synthesized. All of them were characterized by elemental analysis, IR, 1H and 13CNMR . Their conformations are in cone or 1,3-alternate.2. The inclusion complex between 4 and tetrabutyl ammonium bromide(TBAB), L4-TBAB has been obtained and characterized by DTA-TG and XRD analyses. The results obtained indicate that L4-TBAB can be considered as anintramolecular inclusion complex. The PVC membrane ion-selective electrode based on compound 4 as carrier and DOS as plastizer exhibits near Nerstain response characteristic towards quaternary ammonium cation with high selectivity.3. The properties of sensitizing luminescence of Tb3+ by compounds 4-13 were studied and compared with those of compounds 14-17. The results obtained indicate that the compounds 7,12,13 containing phenyl carboxy group have the most remarkable effect on the sensitizing luminescence of Tb3+ among the nine compounds. It could be assumed that the phenyl carboxy group and calix backbone can absorb the energy of ultraviolet and then effectively transmit it to Tb3+. The sensitizing luminescence by O-[w-(carboxyl)benzyl] substituted calix[4]arenes were much better than that by 0-[o-( carboxyl) benzyl] substituted calix[4]arenes. The efficiency of sensitizing luminescence is related to both the steric hindrance of the ligands and the stability of the complexes of Tb3+.4. The crystal structures of intramolecular inclusion complexes L4-CH3CN L4 CH3NO2 L5-CH3CN L9-CH3N02 and compound 10 were determined. The x-ray crystallographic analysis shows that not only the hosts with C4 symmetry but also with C2 symmetry can be bound stably with the guests containing CH group in the intramolecular inclusion complexes. The CH-7t interactions between the CH group of the guest and the phenyl rings of the calix backbone have been proved to be able to stabilize the intramolecular inclusion complexes formed, but it is independent of the acidity of the guest. The x-ray structrual analysisindicates that one ethyl group in the O-substitutents of each molecule of compound 10 enters into another cavity formed by the phenyl rings of the calix backbone in an orderly way. The CH-u interaction exists between the methyl group and the phenyl ring of the calix backbone which makes the compound 10 has a specially regular arrangement in the crystal packing by self-inclusion.更多还原