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Volumn 121, Issue 15, 1999, Pages 3715-3723

Studies of the electronic structure of metallocene-based second-order nonlinear optical dyes

Author keywords

[No Author keywords available]

Indexed keywords

DYE; METALLOCENE; ORGANOMETALLIC COMPOUND; UNCLASSIFIED DRUG;

EID: 0033594518     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9830896     Document Type: Article
Times cited : (283)

References (59)
  • 1
    • 0004243888 scopus 로고    scopus 로고
    • Bruce, D. W., O'Hare, D., Eds.; Wiley: Chichester, and references therein
    • Marder, S. R. In Inorganic Materials, 2nd ed.; Bruce, D. W., O'Hare, D., Eds.; Wiley: Chichester, 1996, and references therein.
    • (1996) Inorganic Materials, 2nd Ed.
    • Marder, S.R.1
  • 15
    • 0345208202 scopus 로고    scopus 로고
    • note
    • -48 esu is estimated for 1.
  • 21
    • 0344777498 scopus 로고    scopus 로고
    • note
    • We also expect d-d transitions to be present in the visible part of the spectrum. However, we expect these to be very weak compared to the two charge-transfer transitions and to make negligible contribution to the observed optical nonlinearity. Therefore, they are not considered further in our discussion.
  • 24
    • 0344777496 scopus 로고    scopus 로고
    • note
    • He I and He II PE spectra for p-nitrostyrene, Fc[1]1, Fc[1]2, Rc[1]1, and Oc[1]2 are presented as Supporting Information.
  • 30
    • 0345208200 scopus 로고    scopus 로고
    • note
    • Interestingly, the PE spectra of Fc[1]1 and Fc[1]2 are virtually superimposable, except that band B occurs at lower IE in the E-isomer, Fc[1]1. This effect can be attributed to the nonplanar π-system of the Z-isomer leading to a weaker interaction between cyclopentadienyl and p-nitrostyrene π-orbitals; this nonplanarity is evident in the crystal structure reported in ref 4.
  • 31
    • 0344777494 scopus 로고    scopus 로고
    • Department of Theoretical Chemistry, Vrije Universiteit, Amsterdam
    • Baerends, E. J.; te Velde, G. ADF, version 2.0.1; Department of Theoretical Chemistry, Vrije Universiteit, Amsterdam, 1996.
    • (1996) ADF, Version 2.0.1
    • Baerends, E.J.1    Te Velde, G.2
  • 35
    • 0345208199 scopus 로고    scopus 로고
    • note
    • Low concentrations had to be employed to avoid polymerization on the electrode.
  • 37
    • 0345640162 scopus 로고    scopus 로고
    • note
    • The unusually large g-factor (2.0056 vs 2.00479 in the nitrobenzene radical anion) and the small hyperfine couplings (a = 0.213 G) to the protons in the 2-position of the ferrocen-1-yl unit also indicate some (very limited) delocalization of spin density onto the ferrocene donor.
  • 42
    • 0345640160 scopus 로고    scopus 로고
    • note
    • Interestingly, the difference in ease of oxidation between Fc″[1]2 (-270 mV vs ferrocenium/ferrocene) and the parent octamethylferrocene (-360 mV) is somewhat larger than that between Fc[1]2 (+25 mV) and ferrocene (0 mV). This reflects the greater contribution of charge-transferred resonance structures to the ground state in the stronger donor (octamethylferrocenyl) case.
  • 43
    • 0344345648 scopus 로고    scopus 로고
    • note
    • 6).
  • 44
    • 0345640159 scopus 로고    scopus 로고
    • note
    • 4 comparison; therefore, it is not surprising that the two bands do not show as similar shifts to one another as in that comparison.
  • 49
    • 0344777493 scopus 로고    scopus 로고
    • note
    • xy orbilals (M), which are unaffected by the bridge planarity. These results are also consistent with the UV-PES data for Fc[1]1 and Fc[1]2.
  • 55
    • 0344777491 scopus 로고    scopus 로고
    • note
    • Spectra showing the solvatochromism of Fc″[3]6 are presented in the Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.