Modulation of Phenol Oxidation in Cofacial Dyads
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CitationKoo, Bon Jun, Michael Huynh, Robert L. Halbach, JoAnne Stubbe, and Daniel G. Nocera. 2015. “Modulation of Phenol Oxidation in Cofacial Dyads.” Journal of the American Chemical Society 137 (37) (September 23): 11860–11863. doi:10.1021/jacs.5b05955.
AbstractThe presentation of two phenols on a xanthene backbone is akin to the tyrosine dyad (Y730 and Y731) of ribonucleotide reductase. X-ray crystallography reveals that the two phenol moieties are cofacially disposed at 4.35 Å. Cyclic voltammetry (CV) reveals that phenol oxidation is modulated within the dyad, which exhibits a splitting of one-electron waves with the second oxidation of the phenol dyad occurring at larger positive potential than that of a typical phenol. In contrast, a single phenol appended to a xanthene exhibits a two-electron (ECE) process, consistent with reported oxidation pathways of phenols in acetonitrile. The perturbation of the phenol potential by stacking is reminiscent of a similar effect for guanines stacked within DNA base pairs.
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