{"title":"Electroprecipitating the Sulfate Radical Anion Amplifies Electrochemiluminescence in Space and Time","authors":"Brady R. Layman, Jeffrey E. Dick","doi":"10.1021/jacs.4c07852","DOIUrl":null,"url":null,"abstract":"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, S<sub>2</sub>O<sub>8</sub><sup>2–</sup>, and tris(bipyridine)ruthenium(II), [Ru(bpy)<sub>3</sub>]<sup>2+</sup> 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 SO<sub>4</sub><sup>•–</sup>, allowing detailed mechanistic insight. We demonstrate platform generalizability by precipitating a radical salt made of calcium and SO<sub>4</sub><sup>•–</sup>, 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.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c07852","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
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, S2O82–, 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.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.