Adaptive molecular quaternary clips made with pyrene functionalized polyhedral oligomeric silsesquioxane.

Evolving synthetic molecules toward complex structures is a major goal in supramolecular chemistry. Increasing the number of clips in a unimolecular multi-clip (UMC), although vital to elevate the complexity of supramolecular architectures, often prevents the UMC from forming host-guest complexes in the bulk phase. To overcome this difficulty, adaptive chemistry was applied to develop a novel adaptive unimolecular quaternary clip (Q-clip). The Q-clip is intrinsically amorphous, but self-organizes with exclusively 4 eq. of allosteric activators (NDI) to form the Q-clip : NDI 4 complexes and a supramolecular lamellar structure in the bulk. The adaptive assembly is fast and allows us to locate the adaptive assembly area of Q-clip : NDI 4 complexes in the amorphous Q-clip film. Our results provide new insights into the design of adaptive UMCs for the evolution toward complex structures and supramolecular functional materials.