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Volumn 129, Issue 19, 2007, Pages 6117-6129

Solvent tuning from normal to inverted marcus region of intramolecular electron transfer in ferrocene-based organic radicals

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTROSCOPY; CHLORINE COMPOUNDS; DATA ACQUISITION; ELECTRON TRANSITIONS; ENERGY BALANCE; GROUND STATE; SOLVENTS;

EID: 34249110291     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja066351g     Document Type: Article
Times cited : (85)

References (128)
  • 9
    • 0004122810 scopus 로고    scopus 로고
    • Balzani, V, Ed, Wiley-VCH: Weinheim
    • (c) Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley-VCH: Weinheim, 2001.
    • (2001) Electron Transfer in Chemistry
  • 59
    • 34249101749 scopus 로고    scopus 로고
    • The exact assignment of the bands is possible considering solvatochromic and electrochemical data obtained in different solvents and the orbital energy scheme of Model 3 described by Barlow et al, see ref 24 and the Supporting Information
    • The exact assignment of the bands is possible considering solvatochromic and electrochemical data obtained in different solvents and the orbital energy scheme of Model 3 described by Barlow et al.; see ref 24 and the Supporting Information.
  • 68
    • 34249108426 scopus 로고    scopus 로고
    • In order to calculate exactly such experimental parameters, some simulations of such absorption bands have been performed by using the TableCurve Software
    • In order to calculate exactly such experimental parameters, some simulations of such absorption bands have been performed by using the TableCurve Software.
  • 69
    • 34249098206 scopus 로고    scopus 로고
    • For all the band shape analysis, an epsilon vs wavenumber [cm -1] representation of the absorption spectra has to be used, since in this way a linear relationship with the energy is obtained
    • -1] representation of the absorption spectra has to be used, since in this way a linear relationship with the energy is obtained.
  • 80
    • 34249105983 scopus 로고    scopus 로고
    • Asymmetry in the band shape of Class II systems mostly arises from additional contributions of transitions from low-lying vibrational levels. An exact band shape analysis affords a quantum mechanical treatment Franck-Condon analysis, which is ongoing work in our research group; see ref 38
    • Asymmetry in the band shape of Class II systems mostly arises from additional contributions of transitions from low-lying vibrational levels. An exact band shape analysis affords a quantum mechanical treatment (Franck-Condon analysis), which is ongoing work in our research group; see ref 38.
  • 81
    • 0008929620 scopus 로고
    • (a) Day, P. Endeavour 1970, 29, 45.
    • (1970) Endeavour , vol.29 , pp. 45
    • Day, P.1
  • 92
    • 34249072371 scopus 로고    scopus 로고
    • 0 is calculated to be 6.17 and 6.38 Å for compounds 1 and 2, respectively. The use of an effective spherical radius is a clear simplification in the case of the complex molecular geometries studied here.
    • 0 is calculated to be 6.17 and 6.38 Å for compounds 1 and 2, respectively. The use of an effective spherical radius is a clear simplification in the case of the complex molecular geometries studied here.
  • 104
    • 34249008874 scopus 로고    scopus 로고
    • Usually the following values are used for such corrector parameter: δ, 0.0 for non-chlorinated aliphatic solvents, δ, 0.5 for polychlorinated aliphatic solvents, and δ, 1 for aromatic solvents
    • Usually the following values are used for such corrector parameter: δ = 0.0 for non-chlorinated aliphatic solvents, δ = 0.5 for polychlorinated aliphatic solvents, and δ = 1 for aromatic solvents.
  • 112
    • 34249087260 scopus 로고    scopus 로고
    • Two solvents were discarded in the LSER treatments of dyads 1 and 2 given in Table S1, since they do not follow the general trends of other solvents, probably because of the presence of impurities; see ref 52
    • Two solvents were discarded in the LSER treatments of dyads 1 and 2 given in Table S1, since they do not follow the general trends of other solvents, probably because of the presence of impurities; see ref 52.
  • 113
    • 34249031062 scopus 로고    scopus 로고
    • For the calculations, we have used α, β, and π* parameters from ref 45 since they were derived under the same conditions. Despite using parameters from different sources for the multiple regression analysis, very similar results have been obtained.
    • For the calculations, we have used α, β, and π* parameters from ref 45 since they were derived under the same conditions. Despite using parameters from different sources for the multiple regression analysis, very similar results have been obtained.
  • 114
    • 34249079885 scopus 로고    scopus 로고
    • SYSTAT for Windows, Version 5; SYSTAT, Inc, Evanston, IL, 1992
    • (a) SYSTAT for Windows, Version 5; SYSTAT, Inc.: Evanston, IL, 1992.
  • 117
    • 34249090886 scopus 로고    scopus 로고
    • By performing a coefficient analysis of each independent variable, we saw that some of the solvents could be left out of the analysis. From the plotting of the experimental values versus the calculated values, we also found that there were some solvents that do not follow the regression model. After those solvents were eliminated, the resulting fits were much better. For the new fits, the linear regression model was valid, with a significance superior - F = 47, p(0.0001) - obtained in first place. The fit is robust because the sign of each coefficient is maintained for all the different fits considering all solvents.
    • By performing a coefficient analysis of each independent variable, we saw that some of the solvents could be left out of the analysis. From the plotting of the experimental values versus the calculated values, we also found that there were some solvents that do not follow the regression model. After those solvents were eliminated, the resulting fits were much better. For the new fits, the linear regression model was valid, with a significance superior - F = 47, p(0.0001) - obtained in first place. The fit is robust because the sign of each coefficient is maintained for all the different fits considering all solvents.
  • 118
    • 34249059474 scopus 로고    scopus 로고
    • opt are assumed to be the same under both conditions.
    • opt are assumed to be the same under both conditions.
  • 121
    • 34249058859 scopus 로고    scopus 로고
    • It has to be kept in mind that this equation was derived originally for a model describing a Coulombic interaction between isolated ions that are surrounded by a spherical ion atmosphere. Therefore, it can be only an approximation for more complicated organic molecules, where electron delocalization (resonance effects) may also be present. However, it has already been successfully applied for other covalently linked donor-acceptor molecules; see ref 58
    • It has to be kept in mind that this equation was derived originally for a model describing a Coulombic interaction between isolated ions that are surrounded by a spherical ion atmosphere. Therefore, it can be only an approximation for more complicated organic molecules, where electron delocalization (resonance effects) may also be present. However, it has already been successfully applied for other covalently linked donor-acceptor molecules; see ref 58.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.