The nanoscale chemical spaces inherent in various organic and metal-organic cages or porous solids and liquids have been continuously explored for their nanoconfinement effect on selective adsorption and reaction of small gas or organic molecules. Herein, we aim to rationalize the unconventional chemical reactivities motivated by the cage-confined nanospaces in aqueous solutions, where the robust yet permeable nanospaces defined by the open-cages facilitate dynamic guest exchange and unusual chemical reactions. The high positive charges on [(Pd/Pt)6(RuL3)8]28+ nanocages drive imidazole-proton equilibrium to display a significantly perturbed pKa shift, creating cage-defined nanospaces in solution with distinct intrinsic basicity and extrinsic acidity. The supramolecular cage effect plays pivotal roles in elaborating robust solution nanospaces, controlling ingress-and-egress molecular processes through open-cage portals, and endowing nanocages with transition-state stabilization, amphoteric reactivities and the phase transfer of insoluble molecules, thus promoting chemical transformations in unconventional ways. Consequently, a wide application of cage-confined catalysis with anomalous reactivities may be expected based on this kind of open-cage solution medium, which combines cage nanocavity, solution heterogeneity and liquid-phase fluidity to benefit various potential mass transfer and molecular process options.

中文翻译：

---

用于多用途催化的含有碱性笼限制纳米空间的酸性开笼溶液

各种有机和金属有机笼或多孔固体和液体中固有的纳米级化学空间因其对小气体或有机分子的选择性吸附和反应的纳米限制作用而被不断探索。在这里，我们的目标是合理化由笼形限制纳米空间在水溶液中激发的非常规化学反应，其中由开放笼定义的坚固但可渗透的纳米空间促进动态客体交换和不寻常的化学反应。[(Pd/Pt)6(RuL3)8]28+ 纳米笼上的高正电荷驱动咪唑-质子平衡以显示出显着扰动的 pKa 位移，从而在溶液中产生具有明显内在碱性和外在酸度的笼形纳米空间。超分子笼效应在构建稳健的溶液纳米空间中起着关键作用，通过开放笼式入口控制进出分子过程，并赋予纳米笼过渡态稳定性、两性反应性和不溶性分子的相转移，从而以非常规的方式促进化学转化。因此，基于这种结合了笼形纳米腔、溶液异质性和液相流动性的开笼式溶液介质，有望广泛应用具有异常反应性的笼式约束催化，从而有利于各种潜在的传质和分子过程选择。