Abstract: | A branched 8]catenane from an efficient one-pot synthesis (72 % HPLC yield, 59 % isolated yield) featuring the simultaneous use of three kinds of templates and cucurbit6]uril-mediated azide–alkyne cycloaddition (CBAAC) for ring-closing is reported. Design and assembly of the 8]catenane precursors are unexpectedly complex that can involve cooperating, competing and non-influencing interactions. Due to the branched structure, dynamics of the 8]catenane can be modulated in different extent by rigidifying/loosening the mechanical bonds at different regions by using solvent polarity, acid-base and metal ions as the stimuli. This work not only highlights the importance of understanding the delicate interplay of the weak and non-obvious supramolecular interactions in the synthesis of high-order n]catenane, but also demonstrates a complex control of dynamics and flexibility for exploiting n]catenanes applications. |