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Volumn 119, Issue 35, 1997, Pages 8253-8268

Effects of intraligand electron delocalization, steric tuning, and excited-state vibronic coupling on the photophysics of aryl-substituted bipyridyl complexes of Ru(II)

Author keywords

[No Author keywords available]

Indexed keywords

RUTHENIUM COMPLEX;

EID: 0030804279     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971321m     Document Type: Article
Times cited : (260)

References (85)
  • 22
    • 0003900489 scopus 로고
    • Siemens Industrial Automation, Inc.: Madison, WI
    • SMART Area-Detector Software Package; Siemens Industrial Automation, Inc.: Madison, WI, 1995.
    • (1995) SMART Area-Detector Software Package
  • 26
    • 0003528603 scopus 로고
    • Molecular Structure Corporation
    • teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation, 1985 & 1992.
    • (1985) Crystal Structure Analysis Package
  • 47
    • 1842299700 scopus 로고    scopus 로고
    • note
    • The electronic coupling between the two multielectronic states is described by an additional term β, not indicated in eq 4. For the purposes of this discussion, we have assumed that this term is constant.
  • 49
    • 1842327284 scopus 로고    scopus 로고
    • note
    • The homogeneous broadening of the individual vibronic transitions characteristic of these complexes in fluid solution at room temperature suggests that low-frequency modes (including the solvent) can be treated classically in the limit ℏω ≪ kT. This approximation allows for a reduction in the number of fitting parameters and allows each vibronic component to be described by a Gaussian distribution function.
  • 50
    • 1842289665 scopus 로고    scopus 로고
    • note
    • Low-temperature emission spectra in this class of molecules have similar features, implying that there are no dramatic differences in the nature of the vibrational modes that couple to excited-state relaxation.
  • 52
    • 1842296196 scopus 로고    scopus 로고
    • note
    • It should be noted that this calculation effectively describes the energy separation between the ground state and the Franck-Condon state. Factors such as spin-orbit coupling and outer-sphere reorganization are therefore not accounted for.
  • 53
    • 1842415866 scopus 로고    scopus 로고
    • note
    • 0/- half-wave potentials.
  • 55
    • 1842407066 scopus 로고    scopus 로고
    • note
    • While the use of electrochemical data for estimating ZPE differences in these molecules is convenient, it does have its limitations. For example, the fact that spin-orbit coupling is not taken into account makes it difficult to directly ascribe these results to the actual emissive state in question. In addition, neither inner-sphere nor outer-sphere reorganization energies are explicitly accounted for in the electrochemical analysis.
  • 66
    • 0003957648 scopus 로고
    • Eyring, H., Henderson, D., Eds.; Academic Press: New York
    • Levich, V. G. Physical Chemistry: An Advanced Treatise; Eyring, H., Henderson, D., Eds.; Academic Press: New York, 1970; Vol. 9B.
    • (1970) Physical Chemistry: An Advanced Treatise , vol.9 B
    • Levich, V.G.1
  • 68
    • 1842375542 scopus 로고    scopus 로고
    • note
    • 2 at 77 K. We do not necessarily dispute their interpretation for two reasons. First, we believe that a comparison of data between glass and fluid solution is problematic, particularly in the present system where we believe significant molecular motion accompanies excited-state relaxation. Second, given the strongly vibronic nature of this system as evidenced by our data, making a distinction between electronic and geometric factors may not be reasonable. We simply point out that all of our results can be explained quite well in the context of a model in which vibrational factors change significantly, but electronic factors do not.
  • 77
    • 1842327880 scopus 로고    scopus 로고
    • note
    • We adopt a localized picture of the excited state of these molecules under our experimental conditions, i.e., fluid solution.
  • 84
    • 1842288460 scopus 로고    scopus 로고
    • note
    • It should be noted that such a torsional mode would be expected to occur at very low frequency and would be difficult to observe. This mode must become active at some stage to reformulate the canted ground state, but it is unclear whether it plays a role as an acceptor in the relaxation mechanism.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.