Ditopic Covalent Cage for Ion-Pair Binding: Influence of Anion Complexation on the Cation Exchange Rate

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. In the cage: A ditopic covalent cage capable of ion-pair recognition was synthesized. Compared to other hemicryptophane parents, an improvement of the association constants and selectivities was observed. Moreover, the rate of exchange of the tetramethylammonium cation was found to be strongly affected by the prior complexation of a halide ion within the cavity.+image