By using a combination of readily accessible experimental and computational experiments in water, we explored the factors governing the association between polyanionic dyn[4]arene and a series of α,ω-alkyldiammonium ions of increasing chain length. We found that the lock-and-key concept based on the best match between the apolar and polar regions of the molecular partners failed to explain the observed selectivities. Instead, the dissection of the energetic and structural contributions demonstrated that the binding events were actually guided by two crucial solvent-related phenomena as the chain length of the guest increases: the expected decrease of the enthalpic cost of guest desolvation and the unexpected increase of the favourable enthalpy of complex solvation. By bringing to light the decisive enthalpic impact of complex solvation during the binding of polyelectrolytes by inclusion, this study may provide a missing piece to a puzzle that one day could display the global picture of molecular recognition in water.

中文翻译：

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以热函方式润湿锁和钥匙有利于聚电解质结合†

通过在水中进行易于进行的实验和计算实验相结合，我们探索了控制聚阴离子达因[4]芳烃与一系列链长不断增加的α,ω-烷基二铵离子之间缔合的因素。我们发现基于分子伴侣的非极性和极性区域之间的最佳匹配的锁和钥匙概念无法解释观察到的选择性。相反，对能量和结构贡献的剖析表明，随着客体链长的增加，结合事件实际上是由两个关键的溶剂相关现象引导的：客体去溶剂化的焓成本的预期下降和客体去溶剂化的焓成本的意外增加。有利的络合物溶剂化焓。通过揭示复杂溶剂化在聚电解质通过包合物结合过程中的决定性焓影响，这项研究可能会为这个谜题提供一个缺失的部分，有一天可以显示水中分子识别的全局图景。