Regulated Single‐Axis Rotations of a Carbonaceous Guest in a van?der Waals Complex with an Entropy Cost
Regulated Single‐Axis Rotations of a Carbonaceous Guest in a van?der Waals Complex with an Entropy Cost
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具有熵成本的范德华复合体中碳质客体的调节单轴旋转
DOI：
10.1002/asia.201901638
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Isobe Hiroyuki
中科院分区：
文献类型：
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作者：
Matsuno Taisuke;Nakai Yusuke;Maniwa Yutaka;Someya Maki;Sato Sota;Isobe Hiroyuki
在仅由无方向性货车德瓦尔斯力组装的紧密主客体复合物中，客体的独特运动，例如固态惯性旋转，出现了。动态运动的调节是一个重要的元素，要探索这种复合物的新功能，这似乎是很难实现的，因为组装力的非方向性。通过在管状宿主中选择适当的客体形状，可以实现可调节的单轴旋转。具体而言，使椭球体客体沿着主体的圆柱轴站立，这因此导致客体在固体中的单轴旋转。对于固态旋转，旋转频率相当高，但被抑制到10 GHz，这是球形客体的各向同性旋转的1/20。 深入的动力学分析定量地揭示了熵成本是调节动力学的决定性因素。
In a tight host–guest complex assembled solely by nondirectional van der Waals forces, unique motions of the guest, such as solid‐state inertial rotations, emerge. The regulation of dynamic motions is an important element to be explored for novel functions of such complexes, which may be seemingly difficult to achieve because of the nondirectionality of the assembling forces. A regulated, single‐axis rotation was made possible by choosing an appropriate shape of the guest in the tubular host. Specifically, an ellipsoidal guest was made to stand along a cylinder axis of the host, which consequently resulted in single‐axis rotations of the guest in the solid. The rotational frequency was considerably high for solid‐state rotations but was suppressed to 10 GHz, which was 1/20 of the isotropic rotation of a spherical guest. In‐depth kinetic analyses quantitatively revealed that the entropy cost was a determining factor that regulated the dynamics.