| Summary: | The cooperative binding behavior of a face-directed octahedral metal-organic supercontainer featuring one <i>endo</i> cavity and six <i>exo</i> cavities was thoroughly examined in chloroform solution through ultraviolet-visible (UV-Vis) titration technique using two representative drug molecules as the guests. The titration curves and their nonlinear fit to Hill equation strongly suggest the efficient encapsulation of the guest molecules by the synthetic host, which exhibit interesting cooperative and stepwise binding behavior. Based on the control experiments using tetranuclear complex as a reference, it is clear that two equivalents of the guest molecules are initially encapsulated inside the <i>endo</i> cavity, followed by the trapping of six additional equivalents of the drug molecules through six <i>exo</i> cavities (1 eq. per <i>exo</i> cavity), and the remaining guests are entrapped by the external pockets. The results provide an in-depth understanding of the cooperative binding behavior of metal-organic supercontainers, which opens up new opportunities for designing synthetic receptors for truly biomimetic functional applications.
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