Wang Xiao-Zhong, Li Xiao-Qiang, Shao Xue-Bin, Zhao Xin, Deng Peng, Jiang Xi-Kui, Li Zhan-Ting, Chen Ying-Qi
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
Chemistry. 2003 Jun 16;9(12):2904-13. doi: 10.1002/chem.200204513.
A general method has been developed to control the selective rearrangement of Meijer's AADD quadruply hydrogen-bonded homodimers by introducing an additional donor-acceptor interaction. Therefore, one donor-assembling monomer, 1, in which the electron-rich bis(p-phenylene)-34-crown-10 moiety is connected to the hydrogen-bonding moiety, and two acceptor-assembling monomers, 2 and 3, in which the electron-deficient pyromellitic diimide or naphthalene diimide group is incorporated, respectively, are synthesized and characterized. 1H NMR and 2D-NOESY studies show that all these compounds exist as stable homodimers in chloroform. Mixing 1 equiv of 1 with 1 equiv of 2 in chloroform leads to the formation of heterodimers 1.2 in approximately 60 % yield, as a result of the electrostatic interaction between the bis(p-phenylene)-34-crown-10 moiety of 1 and the pyromellitic diimide group of 2. Selective formation of heterodimer 1.3 (>97 %) was achieved by mixing 1 equiv of 1 with 1 equiv of 3 in chloroform which resulted in a strengthened electrostatic interaction between the bis(p-phenylene)-[34]crown-10 moiety of 1 and the naphthalene diimide group of 3. The structures of heterodimers 1.2 and 1.3, which have been characterized by 1H NMR and UV/Vis experiments, reveal a remarkable promoting effect between the donor-acceptor interaction and intermolecular hydrogen-bonding. 1H NMR studies also reveal that heterodimers 1.2 and 1.3 can be fully and partially dissociated by addition of heterocycle 29, leading to the formation of new more robust heterodimers 1.29 and 2.29, or 3.29,respectively, and partially regenerated by subsequent addition of heterocyclic compound 30 through the formation of a new heterodimer 29.30. Heterodimers 1.2 and 1.3 represent a novel class of pseudo[2]rotaxanes constructed by two different noncovalent interactions.
通过引入额外的供体 - 受体相互作用，已开发出一种通用方法来控制迈耶（Meijer）的AADD四重氢键同二聚体的选择性重排。因此，合成并表征了一种供体组装单体1，其中富电子的双（对亚苯基）-34-冠-10部分连接到氢键部分，以及两种受体组装单体2和3，其中分别引入了缺电子的均苯四甲酸二酰亚胺或萘二酰亚胺基团。1H NMR和二维NOESY研究表明，所有这些化合物在氯仿中均以稳定的同二聚体形式存在。在氯仿中将1当量的1与1当量的2混合，由于1的双（对亚苯基）-34-冠-10部分与2的均苯四甲酸二酰亚胺基团之间的静电相互作用，导致约60％产率的异二聚体1.2形成。通过在氯仿中将1当量的1与1当量的3混合，实现了异二聚体1.3的选择性形成（> 97％），这导致1的双（对亚苯基）-[34]冠-10部分与3的萘二酰亚胺基团之间的静电相互作用增强。通过1H NMR和UV / Vis实验表征的异二聚体1.2和1.3的结构揭示了供体 - 受体相互作用与分子间氢键之间的显著促进作用。1H NMR研究还表明，通过添加杂环29，异二聚体1.2和1.3可以完全和部分解离，分别导致形成新的更强健的异二聚体1.29和2.29或3.29，并且通过随后添加杂环化合物30通过形成新的异二聚体29.30而部分再生。异二聚体1.2和1.3代表了一类由两种不同非共价相互作用构建的新型假[2]轮烷。
