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The substitution of cyano groups with ester moieties enhances solubility while maintaining redox reversibility and favorable redox potentials. Here we show that these ester\u2010functionalized, hexasubstituted [3]radialene radical anions dimerize reversibly in water. The dimerization mode is dependent on the substitution pattern and can be switched in solution. Stimuli\u2010responsive behavior is achieved by exploiting an unprecedented tristate switching mechanism, wherein the radical can be toggled between the free radical, a \u03c0\u2010dimer, and a \u03c3\u2010dimer\u2010each with dramatically different optical, magnetic, and redox properties\u2010by changing the solvent environment, temperature, or salinity. The symmetric, triester\u2010tricyano[3]radialene (<jats:bold>3<\/jats:bold>) forms a solvent\u2010responsive, \u03c3\u2010dimer in water that converts to the radical anion with the addition of organic solvents or to a \u03c0\u2010dimer in brine solutions. Diester\u2010tetracyano[3]radialene (<jats:bold>2<\/jats:bold>) exists primarily as a \u03c0\u2010dimer in aqueous solutions and a radical anion in organic solvents. The dimerization behavior of both <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> is temperature dependent in methanol solutions. Dimerization equilibrium has a direct impact on catholyte stability during galvanostatic charge\u2013discharge cycling in static H\u2010cells. Specifically, conditions that favor the free radical anion or \u03c0\u2010dimer exhibit significantly enhanced cycling profiles.<\/jats:p>","DOI":"10.1002\/chem.202302829","type":"journal-article","created":{"date-parts":[[2023,11,16]],"date-time":"2023-11-16T01:19:41Z","timestamp":1700097581000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Simple Air\u2010Stable [3]Radialene Anion Radicals as Environmentally Switchable Catholytes in Water"],"prefix":"10.1002","volume":"30","author":[{"given":"Fuead","family":"Hasan","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of North Carolina at Charlotte  Charlotte NC 28223 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jonathan H.","family":"Gillen","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of North Carolina at Charlotte  Charlotte NC 28223 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amaya T.","family":"Jayaweera","sequence":"additional","affiliation":[{"name":"Department of Chemistry Iowa State University  Ames IA 50010 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"suffix":"Jr.","given":"William D.","family":"McDearmon","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of North Carolina at Charlotte  Charlotte NC 28223 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Arthur H.","family":"Winter","sequence":"additional","affiliation":[{"name":"Department of Chemistry Iowa State University  Ames IA 50010 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9263-5414","authenticated-orcid":false,"given":"Christopher M.","family":"Bejger","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of North Carolina at Charlotte  Charlotte NC 28223 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,12,7]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200803073"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201203119"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201501449"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201606472"},{"key":"e_1_2_8_5_1","first-page":"1","volume":"12","author":"Pan M.","year":"2022","journal-title":"Adv. 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