Photogenerated aryl mesylate and aryl diethyl phosphate radical cations: a time-resolved spectroscopy investigation. (15th June 2022)

• Record Type: Journal Article
• Authors: Bonesi, Sergio M.; Protti, Stefano; Capucciati, Andrea; Fagnoni, Maurizio
• Is Part Of: New journal of chemistry. Volume 46:Number 26(2022)
• Page Start: 12589
• Page End: 12599
• Publication Date: 2022-06-15
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d2nj01755e
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : The photoinduced electron transfer reaction of selected aryl sulfonates and phosphates with K2 S2 O8 in a MeCN water (9 : 1) mixture has been investigated by LFP experiments. Abstract : The monoelectronic oxidation of aryl mesylates and aryl diethylphosphates in an organic/aqueous mixture in the presence of ammonium persulfate was investigated by means of time-resolved spectroscopy. The photoinduced electron transfer (ET) between the photogenerated SO4 ˙ − radical anion and the examined substrates showed rate constants ( k ET ) in the order of 10 9 –10 10 M −1 s −1 and the generated radical cations exhibit a broad absorption band (350–550 nm) with lifetime values in the 7–62 μs range, depending on the nature of the aromatic substituents. A satisfactory correlation between log ( k ET ) and Δ G 0ET demonstrates that the ET process follows the Marcus model.