Syntheses of Supramolecular Capsules with "On-off-type" Switch Functions

具有“开关型”开关功能的超分子胶囊的合成

• 批准号: 06453141
• 负责人: SHINKAI Seiji
• 金额: $ 4.74万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453141/
• 关键词: Inclusion; Molecular recognition; Calixarene; Molecular capsule; Metal recognition; Switch function; 超分子; ホスト・ゲスト化学; 包接化合物

Molecular capsules were synthesized by two different methods. The first method is to connect two upper edges of hemisphere-shaped calix [n] arenes. This methods were considerably difficult because of competition between intra-and intermolecular reactions. The capsule molecules composed of two calix [n] arenes show the enhanced affinity toward guest molecules. The second method is to cap or doubly-bridge one calix [n] arene. Capping of calix [6] arene with 1,3,5-tris (bromomethyl) benzene gave a molecule with a closed inner cavity. Double bridging of calix [8] arene with 1,2-bis (bromomethyl) benzene also gave a capsule molecule. They showed a kinetically suppressed exchange of guest ions and molecules.

采用两种不同的方法合成了分子胶囊。第一种方法是连接半球形杯[n]芳烃的两个上边。由于分子内反应和分子间反应之间的竞争，这种方法相当困难。由两个杯[n]芳烃组成的胶囊分子对客体分子的亲和力增强。第二种方法是将一个杯[n]芳烃封盖或双桥接。杯[6]芳烃用1，3，5-三(溴甲基)苯封盖，得到内腔封闭的分子。杯[8]芳烃与1，2-二(溴甲基)苯的双桥联反应也得到了胶囊分子。它们显示出客体离子和分子的交换受到动力学抑制。

项目成果

A.Ikeda: "On the Origin of High Ionophoricity of 1,3-Alternate Calix[4]arenes:π-Donor Participation in Complexation of Cations and Evidence for Metal-Tunneling through the Calix[4]arene Cavity." Journal of the American Chemical Society. 116. 3102-3110 (19

A.Ikeda：“1,3-替代杯[4]芳烃高离子传递性的起源：π供体参与阳离子络合以及通过杯[4]芳烃空腔的金属隧道效应的证据”。美国化学会。116。3102-3110 (19

P. Lhotak, S. Shinkai: "Calix[n]arene-Powerful Building Block of Supramolecular Chemistry" J. Synth. Org. Chem.53. 963-974 (1995)

P. Lhotak、S. Shinkai：“Calix[n]arene 是超分子化学的强大构建模块”J. Synth。

H. Otsuka, S. Shinkai: "Definitive Evidence for Inhibition of Calix [6]arene Ring Inversion Obtained from 1,3-Xylenyl-bridged Chiral Calix [6]arene" J. Am. Chem. Soc.(印刷中).

H. Otsuka，S. Shinkai：“从 1,3-二甲苯基桥接的 Calix [6] 芳烃中获得的抑制 Calix [6] 芳烃环反转的明确证据”J. Am。

H.Otsuka, S.Shinkai: "Definitive Evidence for Inhibition of Calix [6] arene Ring Inversion Obtained from 1,3-Xylenyl-bridged Chiral Calix [6] arene" J.Am.Chem.Soc.(in press).

H.Otsuka、S.Shinkai：“从 1,3-二甲苯基桥接的手性 Calix [6] 芳烃获得的 Calix [6] 芳烃环反转抑制作用的明确证据”J.Am.Chem.Soc.（出版中）。

P. Lhotak, S. Shinkai: "Calix[n]arenes-Powerful Building Blicks of Supramolecular Chemistry" J. Synth. Org. Chem.53. 963-974 (1995)

P. Lhotak、S. Shinkai：“Calix[n]arenes - 超分子化学的强大构建模块”J. Synth。