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Volumn 121, Issue 16, 1999, Pages 4047-4053

Probing the symmetry of the nonlinear optic chromophore Ru(trans-4,4'- diethylaminostyryl-2,2'-bipyridine)32+: Insight from polarized hyper- Rayleigh scattering and electroabsorption (Stark) spectroscopy

Author keywords

[No Author keywords available]

Indexed keywords

BIPYRIDINE DERIVATIVE; RUTHENIUM COMPLEX;

EID: 0033612011     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9840044     Document Type: Article
Times cited : (113)

References (49)
  • 18
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    • note
    • -30 esu.
  • 24
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    • note
    • 333, and the light is z-polarized, the variance induced in the x direction due to orientational fluctuations is described as follows (where N is the number of chromophores and v is the volume): (Formula Presented)
  • 25
    • 2442746919 scopus 로고    scopus 로고
    • s is essentially constant in the low solute concentration range studied
    • s is essentially constant in the low solute concentration range studied.
  • 26
    • 0030149143 scopus 로고    scopus 로고
    • (b) ref 16
    • This method proved reliable in providing consistent, reproducible results. The quantitative validity of the method as compared to an external standard method has been discussed at length. See, for example: (a) Pauley, M. A.; Guan, H.-W.; Wang, C. H.; Jen, A. K.-Y. J. Chem. Phys. 1996, 104, 7821. (b) ref 16.
    • (1996) J. Chem. Phys. , vol.104 , pp. 7821
    • Pauley, M.A.1    Guan, H.-W.2    Wang, C.H.3    Jen, A.K.-Y.4
  • 31
    • 2442754288 scopus 로고    scopus 로고
    • note
    • The assignment of the 430 nm band as an IL transition is supported by an acid addition experiment. Protonating the ammine nitrogens causes the band to shift to ca. 320 nm while leaving the 510 nm band relatively unperturbed. If the 430 nm band had been MLCT in nature, protonation would have created a better electron acceptor and caused the band to red shift.
  • 35
    • 2442747648 scopus 로고    scopus 로고
    • note
    • The indices on the hyperpolarizability tensor are used to denote coordinates. Numbers are used to describe the relevant tensor components within the molecular framework, and letters are used to describe the components observed within the laboratory frame of reference. A more complete discussion can be found in ref 33.
    • , vol.33
  • 37
    • 2442746184 scopus 로고    scopus 로고
    • note
    • 333. The maximum polarization ratio expected is still 1.5.
  • 39
    • 2442755150 scopus 로고    scopus 로고
    • The internal field was assumed to be 1.3 times the externally applied field
    • The internal field was assumed to be 1.3 times the externally applied field.
  • 42
    • 0031780291 scopus 로고    scopus 로고
    • For a cautionary discussion of deconvolution and "uniqueness of fit" problems in electroabsorption spectroscopy, see: Bublitz, G. U.; Laidlaw, W. M.; Denning, R. G.; Boxer, S. G. J. Am. Chem. Soc. 1998, 720, 6068. In principle, the "uniqueness" problem can be at least partially resolved by utilizing higher order Stark spectroscopy. Unfortunately, we were unable to obtain higher order signals.
    • (1998) J. Am. Chem. Soc. , vol.720 , pp. 6068
    • Bublitz, G.U.1    Laidlaw, W.M.2    Denning, R.G.3    Boxer, S.G.4
  • 44
    • 0001393783 scopus 로고
    • Alternate two-level descriptions are also available, which would increase the values of β calculated here by as much as a constant factor of 4. A full discourse on conventions for NLO can be found in the following: Willens, A.; Rice, J. E.; Burland, D. M.; Shelton, D. P. J. Chem. Phys. 1992, 97, 7590.
    • (1992) J. Chem. Phys. , vol.97 , pp. 7590
    • Willens, A.1    Rice, J.E.2    Burland, D.M.3    Shelton, D.P.4
  • 46
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    • note
    • 2, the expected total contribution would be the same for either assignment.
  • 47
    • 2442738826 scopus 로고    scopus 로고
    • note
    • It is also probable that the changes in dipole moment are not in direct opposition to each other. The transition moments for the IL and MLCT transitions are almost certainly offset by some finite angle (see Scheme 1).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.