Abstract
Heating a solution of the circular bis-p-phenylene-34-crown-10 and a dumbbell-shaped bipyridinium component, terminated at both ends by 4-R- phenyl-bis(4-tert-butyl-phenyl)methane-based stoppers, affords the corresponding [2]rotaxane when R is equal to H, Me, and Et, following the slippage of the macrocycle over the stoppers of the dumbbell. By contrast, no [2]rotaxane is obtained when R is equal to i-Pr. Computational investigations with the AMBER* force field provide an explanation of this dramatic substitutent effect. The phenomenon was simulated by the passage of the bis- p-phenylene-34-crown-10 macrocycle over four 4-R-phenyl-bis(4-tert-butyl- phenyl)methane model stoppers. For R equal to H, Me, Et, and i-Pr, there are two main energy barriers which have to be surpassed in order to permit the passage of the macrocycle over the bulky stoppers. When R is equal to H or Me, the rate-determining step is the passage of the macrocycle over a t-Bu- C6H4- ring. By contrast, when R is equal to Et or i-Pr, the rate- determining step becomes the passage of the macrocycle over the R-C6H4- ring. However, when R is equal to i-Pr, the resulting energy barrier is more than 21 kcal mol-1 higher than in the case of any of the other stoppers. These results are in good agreement with the experimental observations and provide a quantitative explanation for the rigorous size complementarily requirements between macrocycle and stopper which have been observed experimentally.
Original language | English (US) |
---|---|
Pages (from-to) | 9318-9322 |
Number of pages | 5 |
Journal | Journal of the American Chemical Society |
Volume | 120 |
Issue number | 36 |
DOIs | |
State | Published - Sep 16 1998 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry