Sequence Rules the Functional Connections and Efficiency of Catalytic Precision Oligomers

The efficiency of cooperative catalysts is dependent on the probabilities of chance encounter between the different complementary catalytic units. Connecting these catalytic groups along a short flexible oligomeric chain increases these probabilities. Her; we show that the sequence of a catalytic triad precisely positioned along a flexible backbone also strongly matters, with the catalytic activity varying by up to 1 order of magnitude when interchanging two groups in the oligomer sequence. These results are rationalized with molecular graphs computed from molecular dynamics simulations, showing how functional connections between catalytic groups are dependent on sequence order.