Light‐Fueled Non‐Photoisomerized Dissipative Self‐Assembly System Through Transient Radical‐Radical Interactions

Abstract Living organisms inspire intensive exploration of artificial dissipative systems under far‐from‐equilibrium thermodynamics. Light, as an ideal fuel form, offers remote control, spatiotemporal precision, and no chemical waste. However, the energy dissipating mechanism behind current light‐driven system hinges on photoisomerization. This strategy has to trade off the slow, incomplete tautomerization against the needs of rapid, dynamic material response. Here, we report a non‐isomerized, light‐fueled dissipative self‐assembly system based on photoexcited radicalization mechanism. Light can activate dipeptide‐modified naphthalene diimide (NDI‐GV) into high‐energy radical anion NDI‐GV ●− , thus disrupting the initial π‐stacked ribbon architecture and triggering a reconfiguration into homochiral helical nanofibers through spin‐spin interactions among the resulted radicals. In turn, ambient air spontaneously oxidizes NDI‐GV ●− to the ground state for resetting the system, during which an unusual solvent‐involved feedback pathway sustaining the dissipative cycle is uncovered. Shifting light parameters or solvents to tune the kinetics of radical generation and deactivation enables temporal control of the assembly period and lifetime (>10 h). Combining the tunability of phase transition with the photochromism of NDIs, this system can be used for light‐programmed information encryption and spatiotemporal patterning, which would inspire a non‐photoisomerized paradigm of light‐powered dissipative self‐assembly and extend the boundaries of systems chemistry.