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Volumn 104, Issue 43, 2000, Pages 9750-9759

Controlling the conformation changes associated to electron transfer steps through chemical substitution: Intriguing redox behavior of substituted vinylogous TTF

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; CONFORMATIONS; ELECTRON TRANSITIONS; MOLECULAR STRUCTURE; OXIDATION; PHOTOLYSIS; PROBABILITY DENSITY FUNCTION; REDOX REACTIONS;

EID: 0034324749     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp001326x     Document Type: Article
Times cited : (63)

References (84)
  • 24
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    • Conformational Change and Isomerization Associated with Electrode Reactions
    • Bard, A. J., Ed.; Marcel Dekker: New York
    • (a) Evans, D. H.; O'Connell, K. M. Conformational Change and Isomerization Associated with Electrode Reactions. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1986; Vol. 14, pp 113-207.
    • (1986) Electroanalytical Chemistry , vol.14 , pp. 113-207
    • Evans, D.H.1    O'Connell, K.M.2
  • 46
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    • 24b and on extended TTF and found to give a good qualitative description of properties
    • 24b and on extended TTF and found to give a good qualitative description of properties.
  • 47
    • 85037468920 scopus 로고    scopus 로고
    • See for example references 24c, 24d, and 13c
    • (b) See for example references 24c, 24d, and 13c.
  • 51
    • 84961981091 scopus 로고    scopus 로고
    • (b). For a general review about solvation methods see: Cramer, J.; Truhlar, D. G. Chem. Rev. 1999, 99, 2161.
    • (1999) Chem. Rev. , vol.99 , pp. 2161
    • Cramer, J.1    Truhlar, D.G.2
  • 52
    • 85037467945 scopus 로고    scopus 로고
    • pc,1 are for the second and first oxidation peak potentials, respectively
    • pc,1 are for the second and first oxidation peak potentials, respectively.
  • 55
    • 85037460820 scopus 로고    scopus 로고
    • 2FIRT}
    • 2FIRT}.
  • 56
    • 85037477623 scopus 로고    scopus 로고
    • The authors have deposited atomic coordinates for this structure with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, U.K.
    • The authors have deposited atomic coordinates for this structure with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, U.K.
  • 57
    • 85037448095 scopus 로고    scopus 로고
    • Agreement between theoretical expectations and experiments are expected if the structural reorganizations occurring at the level of the second electron transfer for the compounds of 2 have negligible or similar influence
    • Agreement between theoretical expectations and experiments are expected if the structural reorganizations occurring at the level of the second electron transfer for the compounds of 2 have negligible or similar influence.
  • 58
    • 85037480734 scopus 로고    scopus 로고
    • note
    • We are aware that the conformations (especially of the dication species) in the presence of a solvent can be slightly changed from the optimization made in the gas phase. However, optimization in the presence of solvent would have required unrealistic calculation times. This approach was chosen as a compromise between calculation time and precision.
  • 59
    • 85037489892 scopus 로고    scopus 로고
    • note
    • solv,disp.
  • 62
    • 85037474582 scopus 로고    scopus 로고
    • note
    • 35b The similarity between the spectra recorded in flash photolysis and spectroelectrochemical experiments confirmed that the spectra correspond to the radical cations and not to dimers. The concentrations of produced radical cation are typically in the range of a few micromolar in flash photolysis against a millimolar in spectroelectrochemistry. Moreover, considering the bulky substituents and thus the important interplanar separation between successive extended TTF cores, dimerization of radical cations appears to be very unfavorable.
  • 64
    • 0003036282 scopus 로고    scopus 로고
    • and references therein
    • Evans, D. H. Acta Chem. Scand. 1998, 52, 194 and references therein.
    • (1998) Acta Chem. Scand. , vol.52 , pp. 194
    • Evans, D.H.1
  • 65
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    • note
    • 37b Tests performed with Digisim 2.1 and the Marcusian kinetics instead of the Butler-Volmer law lead to negligible differences (lower than 1 mV on the calculated peak potentials).
  • 67
    • 0000821227 scopus 로고
    • Electrochemical reactions
    • Bernasconi, C. F., Ed.; Wiley: New York, 4/E
    • Andrieux, C. P.; Savéant, J.-M. Electrochemical reactions. In Investigations of Rates and Mechanisms; Bernasconi, C. F., Ed.; Wiley: New York, 1986; Vol. 6, 4/E, Part. 2, pp 305-390.
    • (1986) Investigations of Rates and Mechanisms , vol.6 , Issue.2 PART , pp. 305-390
    • Andrieux, C.P.1    Savéant, J.-M.2
  • 69
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    • note
    • -1 has been found to have very little influence on the simulation.
  • 70
    • 85037489785 scopus 로고    scopus 로고
    • The extracted potential values are more inverted that the values of Table 1 because the influence of electron-transfer kinetics has been neglected in the simple treatment of Table 1. Table 1 values have to be considered as a higher border for ΔE° values
    • The extracted potential values are more inverted that the values of Table 1 because the influence of electron-transfer kinetics has been neglected in the simple treatment of Table 1. Table 1 values have to be considered as a higher border for ΔE° values.
  • 77
    • 85037476069 scopus 로고    scopus 로고
    • 44b
    • 44b
  • 79
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    • For more general discussions and comparison about methods for estimating intramolecular reorganization energies, see for example refs 45b-e and references therein.
    • (a) For more general discussions and comparison about methods for estimating intramolecular reorganization energies, see for example refs 45b-e and references therein.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.