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Article Abstract
We report that the chirality inversion kinetics of a trinickel(II) cryptand can be controlled by guest recognition in the cryptand cavity. When the guest was absent, the nickel(II) cryptand underwent a dynamic interconversion between the and forms in solution, preferring the form, with a half-life of = 4.99 min. The / equilibrium is reversed to -favored by binding with an alkali metal ion in the cryptand cavity. The timescale of this inversion kinetics was both notably accelerated and decelerated by the guest binding ( = 0.182 min for K complex; 186 min for Cs complex); thus, the equilibration rate constants differed by up to 1000-fold depending on the guest metal ions. This acceleration/deceleration can be explained in terms of the virtual binding constants at the transition state of the / chirality inversion; K binding more stabilizes the transition state rather than the and forms to result in the acceleration.
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| http://dx.doi.org/10.1126/sciadv.adj5536 | DOI Listing |
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