Department of Chemistry, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033, Japan.
JST, ERATO, Isobe Degenerate π-Integration Project, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033, Japan.
Nat Commun. 2018 May 15;9(1):1907. doi: 10.1038/s41467-018-04325-2.
Dynamics of molecules in the solid state holds promise for connecting molecular behaviors with properties of bulk materials. Solid-state dynamics of [60]fullerene (C) is controlled by intimate intermolecular contacts and results in restricted motions of a ratchet phase at low temperatures. Manipulation of the solid-state dynamics of fullerene molecules is thus an interesting yet challenging problem. Here we show that a tubular host for C liberates the solid-state dynamics of the guest from the motional restrictions. Although the intermolecular contacts between the host and C were present to enable a tight association with a large energy gain of -14 kcal mol, the dynamic rotations of C were simultaneously enabled by a small energy barrier of +2 kcal mol for the reorientation. The solid-state rotational motions reached a non-Brownian, inertial regime with an extremely rapid rotational frequency of 213 GHz at 335 K.
固态分子动力学有望将分子行为与体材料性质联系起来。[60]富勒烯（C）的固态动力学受分子间紧密接触的控制，导致低温下棘轮相的运动受限。因此，操纵富勒烯分子的固态动力学是一个有趣但具有挑战性的问题。在这里，我们表明，管状主体可以使客体的固态动力学从运动限制中释放出来。尽管主体与 C 之间存在分子间接触，以实现紧密结合，并获得-14 kcal/mol 的大能量增益，但通过重新取向的+2 kcal/mol 的小能垒，同时实现了 C 的动态旋转。固态旋转运动达到非布朗、惯性状态，在 335 K 时以 213 GHz 的极快旋转频率旋转。
