Macrocycle breathing in [2]rotaxanes with tetralactam macrocycles |
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| Authors: | Murgu Ivan Baumes Jeffrey M Eberhard Jens Gassensmith Jeremiah J Arunkumar Easwaran Smith Bradley D |
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| Institution: | Department of Chemistry and Biochemistry, 236 Nieuwland Science Hall, University of Notre Dame, Notre Dame, Indiana 46556, United States. |
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| Abstract: | The structural dynamics of two pairs of 2]rotaxanes were compared using variable-temperature NMR. Each rotaxane had a surrounding tetralactam macrocycle with either 2,6-pyridine dicarboxamide or isophthalamide bridging units. Differences were observed in two types of rotational processes: spinning of the phenylene wall units in the surrounding macrocycle of squaraine rotaxanes and macrocycle pirouetting in xanthone rotaxanes. The rotaxanes with macrocycles containing 2,6-pyridine dicarboxamide bridges exhibited higher rotational barriers due to a cavity contraction effect, which disfavored macrocycle breathing. |
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