More importantly, the results reveal that the self-assembly of Octacid4 with its guest is governed by the conformational complementarity between the two molecules not only during the ingress time but also during the priming time, and that the host or guest molecule can adopt, at a cost of lengthening the complexation time, an unpopulated conformation to proceed the self-assembly along a repulsionfree path when its populated conformation is not complementary to the conformation of its partner.