Driving conformational motion in defined off-equilibrium oscillations can be achieved using chemical fuels. When the ultrafast turnstile 1 (k 298 > 10 12 Hz) was fueled with 2-cyano-2phenylpropanoic acid (Fuel 1), the diprotonated rotor [H 2 (1)] 2+ (k 298 = 84.0 kHz) formed as a transient regaining the dynamics of the initial turnstile after consumption of the fuel (135 min). Upon addition of silver(I) (Fuel 2) to turnstile 1, the metastable rotor [Ag 2 (1)] 2+ (k 298 = 1.57 Hz) was initially furnished, but due to a consequentially triggered S N 2 reaction, the Ag + ions were consumed as insoluble AgBr along with regeneration of 1 (within 3 h). The off-equilibrium fast ⇆ slow rotor conversions fueled by acid and silver(I) were directly monitored by fluorescence and 1 H NMR. In addition, metal ion exchange was fueled enabling off-equilibrium oscillations between rotors [Li 2 (1)] 2+ ⇆ [Ag 2 (1)] 2+ . In the end, both sustainability and efficiency of the process were increased in unison by using the interfering proton waste in the formation of a [2]pseudorotaxane.
Three 3-component copper(I)-based slider-on-deck systems served as catalysts for a click reaction showing a higher catalytic activity with increasing sliding speed. Upon addition of brake stones, the motion of the...
A dynamic silver(I)-loaded [2]rotaxane shuttle (k 298 = 135 kHz) was converted allosterically into a conformationally restricted [2]rotaxane due to the creation of a bulky imine in the center of the axle component. Only the dynamic silver(I)-loaded [2]rotaxane was able to catalyze a 6-endo-cyclization reaction, whereas the static one was catalytically quiet. The mechanism of catalyst deactivation was elucidated.
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