Ineffective OH Pinning of the Flipping Dynamics of a Spherical Guest within a Tight-Fitting Tube.,Angewandte Chemie International Edition

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Ineffective OH Pinning of the Flipping Dynamics of a Spherical Guest within a Tight-Fitting Tube.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-06-02 , DOI: 10.1002/anie.202005538
Taisuke Matsuno ₁ , Maki Someya ₁ , Sota Sato ₁ , Satoshi Maeda ₂ , Hiroyuki Isobe ₁

Affiliation

A supramolecular/synthetic method has been devised to affix a sterically hindered substituent onto a fullerene guest encapsulated in a tubular host. A two‐wheeled complex of (C₅₉N)‐(C₅₉N) with a tubular host was oxidatively bisected to afford a C₅₉N⁺ cation captured in the tube. The C₅₉N⁺ cation in the tube was then trapped by ethanol or water, which led to an oxy substituent pinned on the guest. The guest motions within the tube were modulated by the pinned substituent, and up‐and‐down flipping motions were halted by an ethoxy substituent. A hydroxy substituent, however, was ineffective in halting the flipping motions, despite the tight‐fitting relationship between the tubular host and the spherical guest. Theoretical calculations of the dynamics revealed that the flipping motions were assisted by OH‐π hydrogen bonds between the guest and the carbon‐rich wall and that sliding motions of the OH group were also facilitated by deformations of the tube.

中文翻译：

密合管内球形客体的翻转动力学的无效OH钉扎。

已经设计了一种超分子/合成方法，将空间位阻取代基固定在包裹在管状主体中的富勒烯客体上。将（C ₅₉ N）-（C ₅₉ N）与管状主体的两轮复合物氧化平分，得到捕获在管中的C ₅₉ N ⁺阳离子。C ₅₉ N ⁺然后，管子中的阳离子被乙醇或水截留，导致固定在客人身上的氧取代基。管内的客体运动通过固定的取代基进行调节，上下翻转运动通过乙氧基取代基停止。然而，尽管管状主体和球形客体之间的紧密配合关系，羟基取代基并不能有效地阻止翻转运动。动力学的理论计算表明，翻转运动是由客体和富碳壁之间的OH-π氢键辅助的，并且管基的变形也有助于OH基团的滑动运动。

更新日期：2020-08-10

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