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Volumn 109, Issue 41, 2005, Pages 9346-9352

Aromatic amines: A comparison of electron-donor strengths

Author keywords

[No Author keywords available]

Indexed keywords

AMINOPHENYL SYSTEMS; AMINOTHIENYL SYSTEM; CHARGE DENSITIES; DENSITY FUNCTIONAL THEORY;

EID: 27544504734     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp054334s     Document Type: Article
Times cited : (133)

References (125)
  • 63
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    • We have previously pointed out the lack of correlation between ET- and π-donor strengths in the comparison of ferrocene with ruthenocene, and of either metallocene with (dialkylamino)anilines (Barlow, S.; Marder, S. R. Chem. Commun. 2000, 1555).
    • (2000) Chem. Commun. , pp. 1555
    • Barlow, S.1    Marder, S.R.2
  • 64
    • 27544508688 scopus 로고    scopus 로고
    • note
    • 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.
  • 84
    • 27544505474 scopus 로고    scopus 로고
    • note
    • 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.
  • 85
    • 0002504535 scopus 로고    scopus 로고
    • 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.
    • (2000) Chem. Phys. Lett. , vol.327 , pp. 13
    • Malagoli, M.1    Brédas, J.-L.2
  • 92
    • 0043142612 scopus 로고    scopus 로고
    • A value of 7.67 eV has been obtained for the vertical IP of carbazole using PES (Marzinzik, A. L.; Rademacher, P.; Zander, M. J. Mol. Struct. 1996, 375, 117-126). This study also includes AMI calculations; the HOMO according to these is qualitatively similar to that obtained in the present work.
    • (1996) J. Mol. Struct. , vol.375 , pp. 117-126
    • Marzinzik, A.L.1    Rademacher, P.2    Zander, M.3
  • 93
    • 27544472088 scopus 로고    scopus 로고
    • note
    • 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.
  • 104
    • 27544498621 scopus 로고    scopus 로고
    • note
    • 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.
  • 105
    • 27544441850 scopus 로고    scopus 로고
    • note
    • 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.
  • 106
    • 0000440589 scopus 로고
    • 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);
    • (1982) Acta Crystallogr. , vol.B38 , pp. 640
    • Fukuyo, M.1    Hirotsu, K.2    Higuchi, T.3
  • 114
    • 0034306074 scopus 로고    scopus 로고
    • 10c (Borowicz, P.; Herbich, J.; Kapturkiewicz, A.; Anulewicz-Ostrowska, R.; Nowacki, J.; Grampp, G. Phys. Chem. Chem. Phys. 2000, 2, 4275). Bond lengths are in reasonable agreement with those calculated in the present work; however, the trends we observe in the calculated data are more difficult to detect due to the subtleties of the trends and the inevitably limited precision of the X-ray work. The crystallographic data also confirm the highly twisted nature of 8 and 10 systems suggested by the calculations, but we have chosen not to compare exact torsion angles because the X-ray values are subject to intermolecular packing effects not considered in the calculations.
    • (2000) Phys. Chem. Chem. Phys. , vol.2 , pp. 4275
    • Borowicz, P.1    Herbich, J.2    Kapturkiewicz, A.3    Anulewicz-Ostrowska, R.4    Nowacki, J.5    Grampp, G.6
  • 121
    • 84861268737 scopus 로고    scopus 로고
    • (a) SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/.
    • SDBSWeb
  • 125
    • 27544495319 scopus 로고    scopus 로고
    • note
    • 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).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.