Catenanes from catenanes: quantitative assessment of cooperativity in dynamic combinatorial catenation

A series of dynamic combinatorial [2] and [3]catenanes have been prepared. Formation of the [3]catenanes occurs with positive or negative cooperativity, depending on the cyclodextrin homologue. Systems level analysis allows cooperativity to be quantified and MD simulations reveal that cooperativity derives from the extents to which hydrophobic surface area is exposed to the aqueous surroundings.