Beyond Batch Addition: Alternative Chemical Fueling Approaches for Enhanced Control of Dissipative Self‐Assembly

A recent prominent direction in the field of supramolecular chemistry and molecular self‐assembly is developing artificial systems which mimic the energy‐consuming self‐assembled architectures found in nature. These synthetic systems can be driven out‐of‐equilibrium by coupling reaction cycles that convert chemical fuels into waste to self‐assembly processes. However, the majority of chemically fueled systems developed so far operate under batchwise additions of fuel into closed reactors, typically leading to only transient nonequilibrium states which lack the complexity of behavior observed in living systems. More recently, therefore, researchers have begun to move beyond such batch addition methods and to instead explore alternative fueling approaches that aim to achieve enhanced control over dissipative self‐assembly of supramolecular artificial systems. This review focuses on examples of these approaches, showing how moving toward thermodynamically open conditions through the use of semi‐batch and open reactors, combined with sustained fuel supply, provides new opportunities to investigate a variety of phenomena, including nonequilibrium steady states, dynamic adaptability, or spatiotemporal oscillations by maintaining systems in sustained nonequilibrium conditions. The emerging use of diffusion‐controlled conditions to modulate the availability of chemical fuels is also explored, highlighting how sustained concentration gradients and precise spatiotemporal control may be exploited for enhanced assembly control.