Synthesis of Intelligent Molecule and Structural Study for its Molecular Complexes

分子识别化学是分子间键的化学。由于分子水平的识别是生物系统的基本特征，因此广泛的研究集中在这一领域。分子间的相互作用包括疏水相互作用、电荷转移相互作用、静电相互作用、π-π堆积相互作用、氢键作用、离子-偶极相互作用等，要了解分子复合物中起主要作用的相互作用，必须弄清复合物在溶液中的精确结构。我们发展了一种有效的方法来分析一个非常灵活的大环化合物的结构，它利用分子力学计算和芳香环电流的磁各向异性的影响。结果表明，该方法适用于溶液中分子间络合物的结构解析。柔性大环化合物的构象控制是柔性大环化合物研究中最具挑战性的问题之一。通过阳离子的络合作用，我们实现了对具有两个冠醚单元的[m. m]邻环芳的控制。以这种具有两个冠醚单元的[m. m]邻环芳为基本骨架合成了一种变构主体化合物。合成了单脱氧杯[4]芳烃连接的氮杂冠醚。该化合物具有较强的选择性迁移Na~+的能力。杯[5]芳烃具有较宽的疏水空腔。我们利用这种宽腔通过偶极官能团在其上边缘的连接来构建主体分子。进行了具有两个苯甲酸部分的客体分子的合成。它在溶液中结合两个咪唑分子。在MacroModel中使用AMBER力场进行的分子力学计算揭示了一个咪唑鎓离子在阳离子-π相互作用的帮助下与杯芳烃π-壁的疏水空腔中被封装。第二个咪唑鎓离子被两个碳原子束缚，

Chemistry of molecular recognition is the chemistry of intermolecular bond. Since recognition at the molecular level is a fundamental characteristic of biological systems, extensive investigations have been focused on this field. Intermolecular bonds are consist of various interaction, hydrophobic, charge transfer, electrostatic, pi-pi stacking, hydrogen bonding, ion-dipolar interaction and so on. In order to know the main contributing interaction in a molecular complex, it should be clarified the precise structure of the complex in solution. We developed an efficient method for structural analysis of an extremely flexible macrocyclic compound, which utilizes both the molecular mechanics calculation and effect of magnetic anisotropy of aromatic ring current. We have shown that the method can be applicable for the structural elucidation of intermolecular complex in solution. Conformational control for flexible macrocycle is one of the most challenging problems. We attained the control of [m.m]orthocyclophanes having two crown units by complexation of cationic species. Synthetic approach of an allosteric host using this[m.m]orthocyclophanes having two crown units as basic skeleton was carried out. The synthesis of aza-crown ether linked with monodeoxycalix[4]arene was carried out. The compound has potent ability for selective transport of Na cation through organic liquid phase. Calix[5]arene has wider hydrophobic cavity than the smaller congener. We applied this wide cavity for construction of a host molecule by the linkage of dipolar functional groups at its upper rim. Synthesis of the guest molecule having two benzoic acid moieties has carried out. It bound two imidazole molecules in solution. Molecular mechanics calculation using AMBER force field implemented in MacroModel has disclosed that one imidazolium ion is encapsulated in the hydrophobic cavity with an aid of cation-pi interaction to calizarene pi-wall. The second imidazolium ion was bound by the two carbo