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It should, however, be noted that these secondary properties will be influenced by solid-state polarization effects and by solvation effects, which will not necessarily be constant for the molecules examined here. Hence, gas-phase IPs may not correlate precisely with solid-state IPs or with solution electrochemical data.
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Solution electrode potentials provide an alternative estimate of ET-donor strength. However, values from different studies are often difficult to compare due to use of different solvents, or of different reference electrodes. Moreover, many of the amines considered here undergo irreversible oxidation, which makes determination of thermodynamic half-wave potentials problematic.
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85
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0002504535
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The present B3LYP/6-311G** calculations give a better estimate of the IP of triphenylamine than a previous estimate at the B3LYP/6-31G** level (6.420 eV: Malagoli, M.; Brédas, J.-L. Chem. Phys. Lett. 2000, 327, 13). A single-point calculation at the B3LYP/6-311C** level at the B3LYP/6-31G** geometry (6.642 eV) shows that most of the difference is attributable to the larger basis set in the present calculations, rather than to differences in the geometries obtained by the two methods.
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The analogous angles for 10b and 10c are 81.5 and 81.6°, respectively. The HOMOs for these species are strongly localized on the phenothiazine portion of the molecule, whereas the LUMOs are essentially confined to the substituted phenyl rings.
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27544498621
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The bond-length alternation can be defined as BLA = (rC1C2 + rC3C4 + rC4C5 + rC6C1)/4 - (rC2C3 + rC5C6)/2. The thiophene derivatives, 11b and 11c, were excluded from this comparison because 11a shows BLA of a sense reversed relative to this definition, and this BLA is reduced by donor-acceptor interactions.
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105
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27544441850
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The dipole moment is not a particularly useful measure of π-donor strength; although it is affected by the zwitterionic resonance contribution to the ground-state structure, it also depends on local contributions such as the dipoles associated with the thiophene rings of the 9 and 11 systems, and so does not correlate well with other measures.
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106
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0000440589
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Crystal structures of some of the species considered in this paper have been determined: 1a (Fukuyo, M.; Hirotsu, K.; Higuchi, T. Acta Crystallogr. 1982, B38, 640);
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37049068423
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8a (Avendaño, C.; Espada, M.; Ocaña, B.; García- Granda, S.; del Rosario Díaz, M.; Tejerina, B.; Gómez- Beltrán, F.; Martínez, A.; Elgero, J. J. Chem. Soc., Perkin Trans. 2 1993, 1547);
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27544495319
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13C NMR spectrum of the known compound 7b in CDCl3́ for the first time: 190.3 (CHO), 157.4 (anisyl C-O quat), 154.1, 138.9 (anisyl C-N quat), 131.5 (phenylene 3,5), 128.2 (anisyl CH), 127.9 (phenylene C4), 116.9 (phenylene 2,6), 115.2 (anisyl CH), 55.7 (Me).
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