Reinventing Chemiluminescence through Redox-Driven Self-Assembly

Chemiluminescence (CL) typically derives from harvesting the energy released during the cleavage of covalent bonds, wherein molecular substrates are irreversibly consumed to generate electronically excited states. In contrast, regenerative CL seeks to bypass substrate decomposition by using reversible redox processes to produce emissive states, an approach that is largely limited to polypyridyl complexes of Ru(II) and Cr(III). Here, we report a fundamentally distinct chemiluminescence mechanism in which the exergonic reduction of Pt(IV) complexes powers the spontaneous formation of emissive Pt(II) aggregates. Notably, light emission arises not from discrete molecular species but from the self-assembled state, whose electronic structure features a lowered excited-state energy (<i>E</i>_0,0) conducive to radiative decay. The emission spectrum observed during chemical reduction matches that of photoexcited aggregates, confirming that the emissive state is intrinsic to the aggregated Pt(II) architecture. This chemiluminescence occurs without external photoexcitation, and its intensity and persistence depend on the nature of the reductant, ranging from transient flashes to sustained afterglow. These findings unveil a new energy transduction pathway in CL: emission driven by redox-triggered self-assembly, expanding the conceptual and chemical space of chemiluminescence beyond classical molecular luminophores and toward dynamic, structure-responsive materials.