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首页> 外文期刊>Chemistry: A European journal >Calix[4]pyrrole-based heteroditopic ion-pair receptor that displays anion-modulated, cation-binding behavior
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Calix[4]pyrrole-based heteroditopic ion-pair receptor that displays anion-modulated, cation-binding behavior

机译：基于Calix [4]吡咯的异位离子对受体，显示阴离子调节的阳离子结合行为

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A new ditopic ion-pair receptor 1 was designed, synthesized, and characterized. Detailed binding studies served to confirm that this receptor binds fluoride and chloride ions (studied as their tetraalkylammonium salts) and forms stable 1:1 complexes in CDCl_3. Treatment of the halide-ion complexes of 1 with Group I and II metal ions (Li~+, Na~+, K~+, Cs~+, Mg~(2+), and Ca~(2+); studied as their perchlorate salts in CD_3CN) revealed unique interactions that were found to depend on both the choice of the added cation and the precomplexed anion. In the case of the fluoride complex [1?F]- (preformed as the tetrabutylammonium (TBA~+) complex), little evidence of interaction with the K~+ ion was seen. In contrast, when this same complex (i.e., [1?F]~- as the TBA~+ salt) was treated with the Li~+ or Na~+ ions, complete decomplexation of the receptor-bound fluoride ion was observed. In sharp contrast to what was seen with Li~+, Na~+, and K~+, treating complex [1?F]~- with the Cs~+ ion gave rise to a stable, receptor-bound ion-pair complex [C?1?F] that contains the Cs ~+ ion complexed within the cup-like cavity of the calix[4]pyrrole, which in turn was stabilized in its cone conformation. Different complexation behavior was observed in the case of the chloride complex [1?Cl] ~-. In this case, no appreciable interaction was observed with Na ~+ or K~+. In addition, treating [1?Cl]~- with Li~+ produces a tightly hydrated dimeric ion-pair complex [1?LiCl(H_2O)]_2 in which two Li~+ ions are bound to the crown moiety of the two receptors. In analogy to what was seen in the case of [1?F]~-, exposure of [1?Cl]~- to the Cs~+ ion gives rise to an ion-pair complex [C?1?Cl] in which the cation is bound within the cup of the calix[4]pyrrole. Different complexation modes were also observed when the binding of the fluoride ion was studied by using the tetramethylammonium and tetraethylammonium salts.
机译：设计，合成和表征了新的双位离子对受体1。详细的结合研究有助于证实该受体结合氟离子和氯离子（被研究为其四烷基铵盐），并在CDCl_3中形成稳定的1：1络合物。用I和II组金属离子（Li〜+，Na〜+，K〜+，Cs〜+，Mg〜（2+）和Ca〜（2+）处理1的卤化物离子配合物（CD_3CN中的高氯酸盐）揭示了独特的相互作用，发现该相互作用既取决于所添加阳离子的选择，也取决于预配合阴离子的选择。在氟化物络合物[1？F]-（预制成四丁基铵（TBA〜+）络合物）的情况下，几乎没有证据表明与K〜+离子发生相互作用。相反，当用Li +或Na +离子处理相同的络合物（即TBA +盐为[1F]-时），则观察到受体结合的氟离子完全分解。与Li〜+，Na〜+和K〜+形成鲜明对比的是，用Cs〜+离子处理复合物[1？F]〜-产生了稳定的，受体结合的离子对复合物[ C？1？F]含有在杯[4]吡咯的杯状腔内络合的Cs〜+离子，而杯状腔又稳定在其圆锥构象中。在氯化物络合物[1？Cl]〜-的情况下，观察到不同的络合行为。在这种情况下，未观察到与Na〜+或K〜+的明显相互作用。此外，用Li〜+处理[1？Cl]〜-会产生紧密水合的二聚离子对络合物[1？LiCl（H_2O）] _ 2，其中两个Li〜+离子键合到两个受体的冠状部分上。与[1？F]〜-的情况类似，[1？Cl]〜-暴露于Cs〜+离子会形成离子对络合物[C？1？Cl]，其中阳离子结合在杯[4]吡咯的杯内。当使用四甲基铵盐和四乙基铵盐研究氟离子的结合时，还观察到了不同的络合模式。

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