Acidic open-cage solution containing basic cage-confined nanospaces for multipurpose catalysis.
Acidic open-cage solution containing basic cage-confined nanospaces for multipurpose catalysis.
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DOI：
10.1093/nsr/nwab155
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发表时间：
2022-05
影响因子：
20.6
通讯作者：
中科院分区：
文献类型：
--
作者：
多孔有机/配位笼或固/液材料固有的纳米级化学空间因其对小气体或有机分子选择性吸附和反应的纳米限制效应而不断被探索。在这里，我们的目标是合理化的非常规化学反应性的笼限定的纳米空间在水溶液中，其中强大的但可渗透的纳米空间所定义的开放笼促进动态的客人交换和不寻常的化学反应。[（Pd/Pt）6（RuL 3）8]28+纳米笼上的高正电荷驱动咪唑-质子平衡以显示显著扰动的pKa位移，从而在溶液中产生具有不同内在碱性和外在酸性的笼限定的纳米空间。超分子笼效应在构建强大的溶液纳米空间，通过开放的笼门控制进出分子过程，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，从而促进非常规方式的化学转化中发挥着关键作用。因此，基于这种开笼溶液介质的笼型催化反应具有广阔的应用前景，它结合了笼型纳米空穴、溶液的非均匀性和液相流动性，有利于各种潜在的传质和分子过程选择。基于具有超分子笼效应的可渗透开放笼，创造了两性和非均相溶液纳米空间，用于超越酶模拟的多角色笼限制催化。
The nanoscale chemical spaces inherent in porous organic/coordination cages or solid/liquid materials 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 range of 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. Amphoteric and heterogeneous solution nanospaces are created on the basis of permeable open cages with supramolecular cage effect for multirole cage-confined catalysis beyond enzyme mimicking.
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影响因子：
29.4
作者：
Jie, Kecheng;Zhou, Yujuan;Nitschke, Jonathan R.
通讯作者：
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影响因子：
21.8
作者：
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影响因子：
64.8
作者：
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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影响因子：
4.3
作者：
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通讯作者：
Nau, Werner M.