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Volumn 107, Issue 44, 2003, Pages 9301-9311

Vibronic Participation of the Bridging Ligand in Electron Transfer and Delocalization: New Application of a Three-State Model in Pyrazine-Bridged Mixed-Valence Complexes of Trinuclear Ruthenium Clusters

Author keywords

[No Author keywords available]

Indexed keywords

DELOCALIZATION;

EID: 0242657917     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp035643q     Document Type: Article
Times cited : (46)

References (74)
  • 9
    • 0242687268 scopus 로고    scopus 로고
    • The Creutz-Taube Ion: Electronic Structure of an Archetypal Mixed-Valence Complex
    • Meyer, T. J., Ed.; Kluwer Academic Publishers: New York (in press)
    • Hupp, J. T. The Creutz-Taube Ion: Electronic Structure of an Archetypal Mixed-Valence Complex. In Comput. Coord. Chem. II; Meyer, T. J., Ed.; Kluwer Academic Publishers: New York (in press).
    • Comput. Coord. Chem. II
    • Hupp, J.T.1
  • 15
  • 52
    • 0242687265 scopus 로고    scopus 로고
    • note
    • The cluster breathing mode that best represents the bond-length adjustments made to a Ru trinuclear cluster upon electron transfer is expected to resemble the fully symmetric cluster breathing mode, but with opposite Ru-C(carbonyl) and Ru-N bond length changes. This ET-associated motion is expected to have a low frequency (but probably not quite as low) similar to that of the fully symmetric cluster breathing mode.
  • 53
    • 0242518577 scopus 로고    scopus 로고
    • note
    • It is not necessarily clear that asymmetric bridge vibrations should have a role similar to that of the asymmetric cluster breathing or cluster-bridging ligand stretching modes.
  • 56
    • 0242687264 scopus 로고    scopus 로고
    • note
    • -1 in 1-4) has not been possible in either infrared or Raman spectroscopy due to specific experimental issues (see section 7).
  • 57
    • 0242687266 scopus 로고    scopus 로고
    • note
    • The near-infrared spectrum of the (-1) state of this "monomeric" cluster exhibits two overlapping bands that presumably have mixed cluster-to-ligand charge-transfer character and should be vibronically coupled to both symmetric cluster breathing modes and symmetric pyrazine breathing modes. Resonance Raman spectroscopy in these bands is expected to confirm vibronic coupling to symmetric pyrazine modes.
  • 59
    • 0242518576 scopus 로고    scopus 로고
    • note
    • - presents the disadvantage of only one allowed electronic transition and requires a to be estimated from other measurements.
  • 60
    • 0242687263 scopus 로고    scopus 로고
    • note
    • Both cluster breathing and cluster-bridging ligand stetching modes should be important to the cluster-to-cluster ET process, and for best accuracy they should both be explicitly considered. The simplified model used in section 5 only includes a single intramolecular ET coordinated for graphical purposes.
  • 61
    • 0242435053 scopus 로고    scopus 로고
    • note
    • - and because the favorable spatial overlap between cluster and bridging ligand orbitals is identical, it can be assumed that for small variations in α, the main influence of varying the ancillary ligand L is a changing α and adjustments to J can be overlooked.
  • 64
    • 0242518575 scopus 로고    scopus 로고
    • note
    • 74 that Marcus-Hush potential surfaces with applied solvent friction cannot predict the fast ET rates observed by carbonyl infared band coalescence.
  • 74
    • 0242435052 scopus 로고    scopus 로고
    • Personal communications
    • Maroncelli, M. P. Personal communications.
    • Maroncelli, M.P.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.