Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, PR China.
J Org Chem. 2013 Jun 7;78(11):5357-63. doi: 10.1021/jo400519z. Epub 2013 May 15.
The highly affinitive and selective binding processes of tetrasulfonated 1,5-dinaphtho-38-crown-10 (1(4-)) and tetrasulfonated 1,5-dinaphtho-32-crown-8 (2(4-)) with pyromellitic diimide and naphthalene diimide derivatives bearing cationic terminal groups (PMDI(2+) and NDI(2+)) are comprehensively investigated in aqueous solution by (1)H NMR and UV/vis experiments, mass spectrometry, microcalorimetric titration, and crystallographic analysis. The binding process of host-guest complexation is thermodynamically driven by the large enthalpic gain and favorable entropic change with the high association constants in the range of 10(4)-10(6) M(-1) order of magnitude. Combined with our previously reported thermodynamic data of ethyl viologen (EV(2+)), it is found that the exclusively selective binding behaviors originate from the size/shape matching effect, as well as the electrostatic interaction between negatively charged hosts and positively charged guests and aromatic π-stacking interrelation between electron-rich donors and electron-deficient acceptors.
高度亲和和选择性的四磺化 1,5-二萘并 38-冠-10（1(4-)) 和四磺化 1,5-二萘并 32-冠-8（2(4-)) 与带有正电荷端基的均苯四甲酰亚胺和萘二甲酰亚胺衍生物（PMDI(2+) 和 NDI(2+)) 的结合过程在水溶液中通过 (1)H NMR 和 UV/vis 实验、质谱、微量热滴定和晶体学分析进行了全面研究。主体-客体络合的结合过程由大的焓变和有利的熵变驱动，具有 10(4)-10(6) M(-1) 数量级的高结合常数，从而实现热力学驱动。结合我们之前报道的乙基紫精（EV(2+)) 的热力学数据，发现这种独特的选择性结合行为源于大小/形状匹配效应，以及带负电荷的主体和带正电荷的客体之间的静电相互作用以及富电子给体和缺电子受体之间的芳香 π-堆积相互关系。
