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Ineffective OH Pinning of the Flipping Dynamics of a Spherical Guest within a Tight‐Fitting Tube
Author(s) -
Matsuno Taisuke,
Someya Maki,
Sato Sota,
Maeda Satoshi,
Isobe Hiroyuki
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202005538
Subject(s) - substituent , chemistry , supramolecular chemistry , crystallography , hydrogen bond , tube (container) , stereochemistry , chemical physics , materials science , composite material , molecule , crystal structure , organic chemistry
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 (C 59 N)‐(C 59 N) with a tubular host was oxidatively bisected to afford a C 59 N + cation captured in the tube. The C 59 N + 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.