Host–guest architectures provide ideal systems for investigating site-specific physical and chemical effects. Condensation events in nanometer-sized confinements are particularly interesting for the investigation of intermolecular and molecule–surface interactions. They may be accompanied by conformational adjustments representing induced fit packing patterns. Here, we report that the symmetry of small clusters formed upon condensation, their registry with the substrate, their lateral packing, and their adsorption height are characteristically modified by the packing of cycloalkanes in confinements. While cyclopentane and cycloheptane display cooperativity upon filling of the hosting pores, cyclooctane and to a lesser degree cyclohexane diffusively redistribute to more favored adsorption sites. The dynamic behavior of cyclooctane is surprising at 5 K given the cycloalkane melting point of >0 °C. The site-specific modification of the interaction and behavior of adsorbates in confinements plays a crucial role in many applications of three-dimensional porous materials as gas storage agents or catalysts/biocatalysts.

中文翻译：

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5 K 纳米级限制内环烷烃的诱导拟合和迁移率

主客架构为研究特定地点的物理和化学效应提供了理想的系统。纳米级限制中的凝聚事件对于研究分子间和分子-表面相互作用特别有趣。它们可能伴随着代表诱导贴合包装模式的构象调整。在这里，我们报告了冷凝后形成的小簇的对称性、它们与底物的配准、它们的横向堆积和它们的吸附高度，它们的特征是通过限制环烷烃的堆积来改变的。虽然环戊烷和环庚烷在填充宿主孔时表现出协同性，但环辛烷和较小程度的环己烷会扩散重新分布到更有利的吸附位点。鉴于环烷烃的熔点 > 0 °C，环辛烷的动态行为在 5 K 时令人惊讶。限制条件下吸附物的相互作用和行为的位点特异性修饰在三维多孔材料作为储气剂或催化剂/生物催化剂的许多应用中起着至关重要的作用。