Electroprecipitating the Sulfate Radical Anion Amplifies Electrochemiluminescence in Space and Time

We have discovered a strategy to synthesize reactive radical salts, effectively bottling up radicals in space and time for future use. We apply this new principle to electrochemiluminescence (ECL) through the simultaneous electro-reduction of peroxydisulfate, S₂O₈^2-, and tris(bipyridine)ruthenium(II), [Ru(bpy)₃]²⁺ in a water/acetonitrile mixture. The electrode generates a concentration profile exceeding the solubility of the cation and anion pair, promoting precipitation. After the application of a potential, leads are disconnected, and the crystals electrolessly chemiluminesce during dissolution and can be transported to other solutions for later chemiluminescence uses. Our method extends ECL hundreds of micrometers from the electrode surface and increases the ECL lifetime by orders of magnitude. Control experiments, including electron spin resonance, validate the crystallization of SO₄^•-, allowing detailed mechanistic insight. We demonstrate platform generalizability by precipitating a radical salt made of calcium and SO₄^•-, and we demonstrate the salt's ability to drive chemiluminescence. Our results emphasize the elegant chemical tenet that extremely reactive radicals can be bottled up as solids to be used as future reagents if precipitation occurs more quickly than the radical lifetime.