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2242473317
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note
-
For synthetic details see the Supporting Information. A similar oxidation reaction giving the TTF radical cation salt was also observed under these conditions for 4-hydroxymethyl-TTF (ref 37).
-
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42
-
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2242477871
-
-
note
-
Only two reversible reductions have been observed for 19.
-
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-
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44
-
-
2242464318
-
-
note
-
CVs for the scan rates from 0.1 to 1.0 V only are shown on Figure 3 for clarity.
-
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-
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46
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An inversion of the standard potentials for the first and second electron transfer substantially depends on the structure of carotenoids: an inversion occurs in the oxidation of β-carotene and in the reduction of canthaxanthin, but not in the reduction of β-carotene or in the oxidation of canthaxanthin: Hapiot, P.; Kispert, L. D.; Konovalov, V. V.; Savéant. J.-M. J. Am. Chem. Soc. 2001, 123, 6669-6677.
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2242437501
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note
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0 species) and at low electrolyte concentration (to prevent its precipitation at low temperatures).
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Chapman and Hall: London and New York
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-1 as an extremely weak band. Variation of the solvent did not restore the peak intensity. A marked variation in the intensity of CN absorption from strong to undetectable in different solvents and with the incorporation of certain substituents is well documented: Bellamy, L. J. In The Infrared Spectra of Complex Molecules, 3rd Ed.; Chapman and Hall: London and New York, 1975; Vol. 1, p 297.
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2242423055
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note
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2 only. Given its very low concentration and the fact that it disappears on changing the solvent, concentration, or temperature, we cannot unambiguously assign this signal.
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2242463440
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note
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The free radical concentration in the solid state was estimated at 298 K by spin counting experiment to be ca. 15%, as a result of antiferromagnetic interaction between neighboring fluorene moieties. Lowering of the observed spin number (in respect to the theoretical value) is typical for many radical ion salts, e.g., ref 3b.
-
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60
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2242493015
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-
note
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+, precludes observation of the smaller couplings.
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2242436606
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-
note
-
Fast scanning of the potential with continuous recording of the spectra was employed as a practically achievable alternative to time-resolved pulse SEEPR.
-
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63
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0000402838
-
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Reference 16d
-
Although formation of cation radical also yields one aromatic dithiolium ring, the largest gain of aromaticity occurs on transition from cation radical (which essentially preserves the geometry of the neutral species) to fully aromatic dication: (a) Reference 16d. (b) Martín, N.; Sánchez, L.; Seoane, C.; Ortí, E.; Viruela, P. M.; Viruela, R. J. Org. Chem. 1998, 63, 1268-1279.
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64
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0000402838
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Although formation of cation radical also yields one aromatic dithiolium ring, the largest gain of aromaticity occurs on transition from cation radical (which essentially preserves the geometry of the neutral species) to fully aromatic dication: (a) Reference 16d. (b) Martín, N.; Sánchez, L.; Seoane, C.; Ortí, E.; Viruela, P. M.; Viruela, R. J. Org. Chem. 1998, 63, 1268-1279.
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0023643219
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2242421295
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note
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The low accuracy accompanying measurements of such weak bands does not exclude the possibility that intermolecular complexation may contribute to these absorption bands.
-
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72
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2242453601
-
-
note
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2+ does not absorb beyond 600 nm (ref 16d).
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-
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73
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2242493014
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Reference 21
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All the known X-ray crystal structures of nitrofluorene-TTFs CTCs are neutral or have only partial charge transfer: (a) Reference 21.
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74
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(b) Perepichka, I. F.; Perepichka, D. F.; Lyubchik, S. B.; Bryce, M. R.; Batsanov, A. S.; Howard, J. A. K. J. Chem. Soc., Perkin Trans. 2 2001, 1546-1551.
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Veciana, J., Rovira, C., Amabilino, D. B., Eds.; NATO ASI Series; Kluwer Publishers: Dordrecht
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(c) Bryce, M. R.; Moore, A. J.; Batsanov, A. S.; Howard, J. A. K.; Robertson, N. R.; Perepichka, I. F. In Supramolecular Engineering of Synthetic Metallic Materials: Conductors and Magnets; Veciana, J., Rovira, C., Amabilino, D. B., Eds.; NATO ASI Series; Kluwer Publishers: Dordrecht, 1999; Vol. 518, pp 437-449.
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81
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2242472421
-
-
note
-
2 (1.487(6) Å) (ref 16e).
-
-
-
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83
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0001294785
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(b) Kistenmacher, T. J.; Emge, T. J.; Bloch, A. N.; Cowan, D. O. Acta Crystallogr. 1982, B38, 1193-1199.
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2242419467
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Moore, A. J.; Chesney, A.; Bryce, M. R.; Batsanov, A. S.; Kelly, J. F.; Howard, J. A. K.; Perepichka, I. F.; Perepichka, D. F.; Meshulam, G.; Berkovich, G.; Kotler, Z.; Mazor, R.; Khodorkovsky, V. Eur. J. Org. Chem. 2001, 1927-1935.
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-
87
-
-
2242420359
-
-
note
-
2, mp 158-160 °C.
-
-
-
-
88
-
-
2242459857
-
-
note
-
Hydrolysis of compound 10 to fluorenone 9 on silica (which we have not observed for other fluorene-9-dicyanomethylene derivatives) does not allow chromatographic purification.
-
-
-
-
89
-
-
2242465197
-
-
note
-
2 to elute all the compound.
-
-
-
-
91
-
-
0001313650
-
-
Procedure adapted from: Andrievskii, A. M.; Gorelik, M. V.; Avidon, S. V.; Al'tman, E. Sh. Russ. J. Org. Chem. 1993, 29, 1519-1524; Zh. Org. Khim. 1993, 29. 1828-1834 (in Russian).
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-
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Andrievskii, A.M.1
Gorelik, M.V.2
Avidon, S.V.3
Al'tman, E.Sh.4
-
92
-
-
0001405569
-
-
in Russian
-
Procedure adapted from: Andrievskii, A. M.; Gorelik, M. V.; Avidon, S. V.; Al'tman, E. Sh. Russ. J. Org. Chem. 1993, 29, 1519-1524; Zh. Org. Khim. 1993, 29. 1828-1834 (in Russian).
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(1993)
Zh. Org. Khim.
, vol.29
, pp. 1828-1834
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-
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