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3C group diminishes it. (This hypothesis is the subject of ongoing computational study.) The proposed ICT excited state bears resemblance to a sulfoxide radical cation, and we note that single-electron oxidation of enantiomerically enriched aryl sulfoxides dramatically increases rates of sulfoxide racemization - 1942
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3C group diminishes it. (This hypothesis is the subject of ongoing computational study.) The proposed ICT excited state bears resemblance to a sulfoxide radical cation, and we note that single-electron oxidation of enantiomerically enriched aryl sulfoxides dramatically increases rates of sulfoxide racemization: Aurisicchio, C.; Baciocchi, E.; Gerini, M. F.; Lanzalunga, O. Org. Lett. 2007, 9, 1939-1942
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Binding constants were determined by nonlinear least-squares fitting of plots of emission intensity vs log[M] using the program Prism6 (Graphpad, Inc. San Diego, CA). All ligand/metal complexes were of 1:1 stoichiometry, as determined by the method of continuous variation. See: John Wiley & Sons: New York
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Binding constants were determined by nonlinear least-squares fitting of plots of emission intensity vs log[M] using the program Prism6 (Graphpad, Inc., San Diego, CA). All ligand/metal complexes were of 1:1 stoichiometry, as determined by the method of continuous variation. See: Connors, K. A. Binding Constants: John Wiley & Sons: New York, 1987.
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While the present system is almost unique in that oxygen coordination leads to a direct perturbation of the excited state of a single chromophore, it must be mentioned that there are other oxygen coordination-based signaling motifs, such as polyether coordination that leads to changes in the degree of excimer formation between two pendant chromophores, or calixarene coordination events that lead to displacement of a chromophore and a subsequent solvatochromic shift in emission. (See refs 1 and 2.) In what may be regarded as the first designed fluorescent chemosensor, crown ethers containing an integrated naphthalene group were found to respond to metal ion binding via changes in fluorescence - 310
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While the present system is almost unique in that oxygen coordination leads to a direct perturbation of the excited state of a single chromophore, it must be mentioned that there are other oxygen coordination-based signaling motifs, such as polyether coordination that leads to changes in the degree of excimer formation between two pendant chromophores, or calixarene coordination events that lead to displacement of a chromophore and a subsequent solvatochromic shift in emission. (See refs 1 and 2.) In what may be regarded as the first designed fluorescent chemosensor, crown ethers containing an integrated naphthalene group were found to respond to metal ion binding via changes in fluorescence: Sousa, L. R.; Larson, J. M. J. Am. Chem. Soc. 1977, 99, 307-310
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