Transient supramolecular assembly of a functional perylene diimide controlled by a programmable pH cycle

Self-regulating materials require embedded control systems. Active networks of enzymes fulfill this function in living organisms, and the development of chemical controls for synthetic systems is still in its infancy. While previous work has focused on enzymatic controls, small-molecule networks have unexplored potential. We describe a simple small-molecule network that is able to produce transient pH cycles with tunable lagtimes and lifetimes, based on coupling the acid-to-alkali methylene glycol-sulfite reaction to 1,3-propanesultone, a slow acid generator. Applied to transient pH-driven supramolecular self-assembly of a perylene diimide, our system matches the flexibility of in vitro enzymatic systems, including the ability to perform repeated cycles of assembly and disassembly. Transient supramolecular self-assembly with tunable lifetime is achieved by coupling an alkali-generating clock reaction to a slow acid generator.