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See ref 15, p 40.
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0344660066
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The CT absorption band of the stilbene/chloranil EDA complex is centered at 510 nm. See ref 18
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The CT absorption band of the stilbene/chloranil EDA complex is centered at 510 nm. See ref 18.
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35
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note
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• → oxetane
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41
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0344660067
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(b) For the observation of 1,4-biradicals from the related benzoquinone and styrene, see:
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0345522392
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note
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27 (direct observation notwithstanding). Accordingly, we focus here on stilbene donors more closely akin to the original Paterno-Büchi substrates from which we could actually isolate the [2+2] cycloadducts and verify their oxetane structures by X-ray crystallography.
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Unpublished results (reported in ref 30b)
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note
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The regiochemistry of the coupling could not be established by GC/MS analysis owing to complete decomposition of the spirooxetanes (to the starting materials) upon their injection into the gas chromatograph.
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65
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0001672288
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With increasing oxidation potentials of the stilbene, the back electron transfer from stilbene cation radical to chloranil anion radical becomes more exergonic, and thus its rate constant will decrease in the Marcus-inverted region. See: (a) Marcus, R. A. Annu, Rev. Phys. Zhem. 1964, 15, 155.
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0344660042
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CT n Table 1.
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74
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0000887799
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Hatchard, C. G.; Parker, C. A. Proc. R. Soc. 1958, 235A, 518. See also: Calvert, J. G.; Pitts, J. N., Jr. Photochemistry; Wiley: New York, 1996, p 786.
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0345090861
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note
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On the early picosecond time scale, the singlet ion-radical pair is observed due to CT excitation of the chloranil/stilbene EDA complex, which also absorbed at 406 nm (vide supra).
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0001635870
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0344228741
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note
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A detailed study of the solvent effects on the back electron transfer, the ion dissociation, and the coupling processes will be published later.
-
-
-
-
90
-
-
0345090860
-
-
note
-
23 is deternined by the relative orientation of the ion-radical pair, particularly is it is affected by the charge distribution. [As such, the spin nultiplicity of the singlet or triplet biradical state does not appear to be a distinguishing factor.] Charge annihilation in the triplet ion-radical pair may proceed either directly to the 1,4-biradical or via spin inversion followed by ion-pair collapse to the singlet 1,4-biradical.
-
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93
-
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0344228739
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note
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47
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94
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0344228740
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note
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On deposit with the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB12 1EZ, U.K.
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96
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0029884141
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