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.