Ineffective OH Pinning of the Flipping Dynamics of a Spherical Guest within a Tight-Fitting Tube |
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Authors: | Dr Taisuke Matsuno Maki Someya Dr Sota Sato Prof Dr Satoshi Maeda Prof Dr Hiroyuki Isobe |
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Institution: | 1. Department of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-0033 Japan;2. Department of Chemistry and Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 10, Nishi 8, Kita-ku, Sapporo, 060-0810 Japan |
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Abstract: | 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. |
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Keywords: | cations fullerenes hydrogen bonds molecular dynamics nanotubes |
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