Wang Xueye, Wang Hengliang, Tan Yuanqiang
Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, People's Republic of China.
J Comput Chem. 2008 Jul 15;29(9):1423-8. doi: 10.1002/jcc.20903.
In the present work, a theoretical study of the cryptand 4, 7, 13, 16, 21, 24-hexaoxa-1, 10- diazabicyclo [8,8,8] hexacosan (the named [222]) and the cryptand 5, 6-benzo-4, 7, 13, 16, 21, 24-hexaoxa-1, 10-diazabicyclo [8, 8, 8] hexacosan (the nemed [222B]) had been done using density functional theory (DFT) with B3LYP/6-31G* method in order to obtain the electronic and geometrical structure of the cryptands and their complexes with alkali metal ions: Li(+), Na(+), and K(+). The nucleophilicity of cryptands had been investigated by the Fukui function. For complexes, the match between cation and cavity size, the status of interaction between alkali metal ions and donor atoms in the cryptands and the rigidity of the cryptands had been analyzed through the other calculated parameters. In addition, the enthalpies of complexation reaction and cation exchange reaction had been studied by the calculated thermodynamic data. The calculated results are in a good agreement with the experimental data for the complexes.
在本工作中，使用密度泛函理论（DFT）的B3LYP/6 - 31G*方法对穴醚4,7,13,16,21,24 - 六氧杂 - 1,10 - 二氮杂双环[8,8,8]二十六烷（命名为[222]）和穴醚5,6 - 苯并 - 4,7,13,16,21,24 - 六氧杂 - 1,10 - 二氮杂双环[8,8,8]二十六烷（命名为[222B]）进行了理论研究，以获得穴醚及其与碱金属离子Li(+)、Na(+)和K(+)形成的配合物的电子结构和几何结构。通过福井函数研究了穴醚的亲核性。对于配合物，通过其他计算参数分析了阳离子与空腔大小的匹配情况、碱金属离子与穴醚中供体原子之间的相互作用状态以及穴醚的刚性。此外，通过计算得到的热力学数据研究了络合反应和阳离子交换反应的焓。计算结果与配合物的实验数据吻合良好。
