化学
四甲基铵
卤化物
部分
离子交换
无机化学
离子
合作性
主客化学
碱金属
离子键合
结晶学
物理化学
超分子化学
立体化学
有机化学
晶体结构
生物化学
作者
Magalie Delecluse,Anne‐Doriane Manick,Bastien Châtelet,Sabine Chevallier‐Michaud,Delphine Moraléda,Innocenzo De Riggi,Jean‐Pierre Dutasta,Alexandre Martinez
标识
DOI:10.1002/cplu.202300558
摘要
A new hemicryptophane host with a ditopic molecular cavity combining a cyclotriveratrylene (CTV) unit with a tris‐urea moiety was synthesized. The complexation of halides, tetramethylammonium (TMA+) cation, and ion pairs was investigated. A positive cooperativity was observed, since halides display a higher binding constant when a TMA cation is already present inside the cage. When TMA was complexed alone, a decrease of temperature from 298 K to 230 K was required to switch from a fast to a slow exchange regime on the NMR time scale. Nevertheless, the prior complexation of a halide guest in the lower part of the host resulted in significant decrease of the exchange rate of the subsequent complexation of the TMA+ cation. Under these conditions, the 1H NMR signals characteristic of a slow exchange regime were observed at 298 K. Addition of an excess of salts, increases the ionic strength of the solution, restoring the fast exchange dynamics. This result provides insight on how the exchange rate of a cation guest can be modulated by the complexation of a co‐guest anion.
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