Carborane Guests for Cucurbit[7]uril Facilitate Strong Binding and On-Demand Removal
Anna Kataki‐Anastasakou, Jonathan C. Axtell, Selena Hernandez, Rafal M. Dziedzic, Gary J. Balaich, Arnold L. Rheingold, Alexander M. Spokoyny, Ellen M. Sletten
Abstract
High-affinity guests have been reported for the macrocyclic host cucurbit[7]uril (CB[7]), enabling widespread applications, but hindering CB[7] materials from being returned to their guest-free state for reuse. Here, we present polyhedral boron clusters (carboranes) as strongly binding, yet easily removable, guests for CB[7]. Aided by a Pd-catalyzed coupling of an azide anion, we prepared boron-functionalized 9-amino-ortho-carborane that binds to CB[7] with a Ka ≈ 1010 M–1. Upon basic treatment, ortho-carborane readily undergoes deboronation to yield anionic nido-carborane, a poor guest for CB[7], facilitating recovery of guest-free CB[7]. We showcase the utility of the modified ortho-carborane guest by recycling a CB[7]-functionalized resin. With this report, we introduce stimuli-responsive decomplexation as an additional consideration in the design of high-affinity host–guest complexes.