Liquid Membrane Transport of Mercury Ion with Troponoid Dithiocrown Ethers and Their Theoretical Analysis

自从冠醚与各种金属离子形成配合物以来，冠醚在主客体化学中发挥了重要作用。与此同时，大量的注意力一直致力于开发新的离子载体，以实现与金属离子的选择性络合。另一方面，环α-二酮的环酚酮烯醇也与金属离子形成络合物。基于这些观察结果，我对冠醚与托品单元的主客体化学感兴趣，它有两个络合位点。在此基础上，合成了具有HgCl_2捕获能力的二硫代冠醚类化合物，并通过X射线晶体学、分子力学和半经验分子轨道计算对它们的配合物结构进行了表征（锚II）在这项研究中，已经进行了托品二硫代冠醚-汞络合物的半经验分子轨道计算（CAChe），对假想分子“托品冠醚”-锂络合物进行了从头算分子轨道计算，发现托品冠醚的羰基在与金属离子的络合中起重要作用。

Crown ethers have playd an important role in host-guest chemistry since the discovery of the formation of their complexes with various metal ions. At the same time, considerable attention has been devoted to the development of new ionophores to achieve selective complexation with metal ions. On the other hand, tropolones enols of a cyclic alpha-diketone also form complexes with metal ions. Based on these observations, I was interested in the host-guest chemistry of the crown ethers with a troponoid unit, which have two complexing sites. Then, I have synthesized Hg^<2+> -capturing dithiocrown ethers of troponoids.So far, the complex structures of the dithiocrown ethers with HgCl_2 were determined by X-ray crystallography, and were estimated by molecular mechanics calculations and semi-empirical molecular orbital calculations (ANCHOR II).In this study, semi-empirical molecular orbital calculations (CAChe) of the troponoid dithiocrown ether-mercury complex have been carried out, and ab initio molecilar orbital calculations have been performed on hypothetical molecule "troponoid crown ether" -lithium complex.Carbonyl group of tropone plays an important role in the complexation with metal ion.