Imine Macrocycle with a Deep Cavity: Guest‐Selected Formation of syn/anti Configuration and Guest‐Controlled Reconfiguration

A dynamic covalent bond is one of the ideal linkages for the construction of large and robust organic architectures. In the present article, we show how organic templates can efficiently transform a complex dynamic imine library into a dynamic imine macrocycle. Not only is the constitution well controlled, but also the syn/anti host configuration is efficiently selected and even the orientation of the guest in the asymmetric cavity of the host can be well aligned. This is attributed to the delicate balance and the cooperation of multiple noncovalent interactions between the hosts and the guests. Through sequential additions of three guests in appropriate amounts, controlled structural reconfiguration of dynamic covalent architectures has been achieved for the first time.