Stark spectroscopy of donor/acceptor substituted polyenes

Journal of the American Chemical Society

Volumn 119, Issue 14, 1997, Pages 3365-3376

  Bublitz, Gerold U ^a   Ortiz, Rafael ^b   Marder, Seth R ^b,c   Boxer, Steven G ^a  

^a STANFORD UNIVERSITY   (United States)

^b CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

^c CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

POLYENE;

ARTICLE; DRUG STRUCTURE; ELECTRON SPIN RESONANCE; MOLECULAR DYNAMICS;

EID: 0030908710     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9640814     Document Type: Article

References (60)

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22. f depends on the dielectric constant (ε) of both the solvent and the solute. A quite realistic approach is to model f by an ellipsoidal dielectric imbedded within another dielectric [Böttcher, C. J. F. Theory of Electric Polarization, 2nd ed.; Elsevier: Amsterdam, 1973; Vol. 1, p 79ff]. For the frozen 2-MeTHF matrix ε can be estimated from capacitance measurements (15) to be about 3.2. ε is unknown for the studied molecules, but should be close to the same value. Using appropriate molecular dimensions of 20 Å × 4 Å × 4 Å and a rather large range of ε between 5.5 and 2 for the studied compounds, the local field correction would be 0.75-1.22 along the short molecular axis and 0.96-1.02 along the long axis. Since the main components of both |Δμ| and Δα lie along the long molecular axis (see text) the local field correction factor will be neglected in the discussion.
23. In calculating |Δμ|, the ratio of ΔA and the second derivative of the absorption spectrum has to be evaluated. Since a broad absorption spectrum gives rise to a rather small second derivative both have to be considered in order to extract molecular parameters.
24. Similar but less pronounced low-energy features are observed in the ΔA spectrum of 5, 6, and 7.
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27. The same phenomenon, although less pronounced, can also be observed for 3, 8, 9, and 10.
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42. The studied compounds contained the dicyano acceptor group (as compounds 2 and 3 in this study) along with a dimethylanilino or a julolidine donor group.
43. This relative independence of the ground state dipole moment and polyene chain length has recently been confirmed in other sets of donor/ acceptor polyenes. Blanchard-Desce, M.; Alain, V.; Midrier, L.; Wortmann, R.; Lebus, S.; Glania, C.; Krämer, P.; Fort, A.; Muller, J.; Barzoukas, M. J. Photochem. Photobiol. A In press.
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47. Since for the compounds studied here the location of the absorption maximum is highly solvent dependent, it can be used to determine the polarity of the frozen solvent matrix. Based on such a comparison we can conclude that for 4, 6, 7, and 8 the polarity of a frozen 2-MeTHF matrix corresponds to a polarity of liquid DMF to DMSO at room temperature. See: Bublitz, G. U.; Ortiz, R.; Runser, C.; Fort, A.; Barzoukas, M.; Marder, S. R.; Boxer, S. G. J. Am. Chem. Soc. 1997, 119, 2311-2312.
48. Bublitz, G. U.; Boxer, S. G. In preparation.
49. 0 is of gerade symmetry, the term for A will be symmetry forbidden. The expression for B on the other hand involves two virtual states i and j. For i having ungerade symmetry and j gerade symmetry this term will be symmetry allowed.
50. u symmetry, we will still use these terms for the two lowest excited states in order to label their main parentage.
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53. j cross terms to the first derivative components of the ΔA spectra (eq 3) which were interpreted as being solely due to Δα. However, assuming a derivative relationship (cf. ref 7) between the main components of the transition hyperpolarizability A and transition moment m, A ∝ dm/dF, and using the calculated evolution of m vs BOA (not shown) and Δμ vs BOA (cf. Figure 8) of ref 9 this cross term is expected to be close to zero around the cyanine limit C. For an increasing polyene-like character of the bridge (i.e. upon going from C toward limit A or E) the relative contribution of the cross terms is predicted to increase. Accordingly, the reported values of Δα might be too large for those molecules assigned close to regions B or D if the absolute magnitude of this contribution turns out to be not negligible. However, since the trends in this calculated evolution of the cross-term contribution vs BOA and of Δα vs BOA are similar (decreasing from A to C, then increasing again), none of the assignments of the compounds (cf. Figure 8) would be affected.
54. g absorption), or it could be due to a direct interaction of the donor and acceptor end groups since the connecting bridge is extremely short in this case.
55. Vauthey, E.; Holliday, K.; Wei, C.; Renn, A.; Wild, U. P. Chem. Phys. 1993, 171, 253-263.
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57. Assuming a maximum deviation of 20% between data and fit in ΔA and attributing all of this change to this origin, |Δμ| will change by maximal ±10% across the inhomogeneously broadened band.
58. Differences, however, do exist between internal electric field effects (such as those produced by the end groups) and external ones (such as those of the solvent matrix) with regard to the heterogeneity of the electrooptic parameters. This was demonstrated in a Stark spectroscopic study of the carotenoid derivative spheroidene which is one of the chromophores of the B800-850 antenna complex protein. [Gottfried, D. S.; Steffen, M. A.; Boxer, S. G. Biochim. Biophys. Acta 1991, 1059, 76-90 and Science 1991, 251, 662-665]. Embedded in a nonpolar organic glass spheroidene shows only moderately small values of |Δμ| < 4.7 D. However, for the same chromophore, now at its position inside the protein, this value changes dramatically and |Δμ| ≈ 15 D for the main absorption peak as well as for all vibronic side bands. This large |Δμ| is apparently due to the effect of the protein matrix on the electronic structure of the chromophore - effectively an external field effect. A comparably large value of |Δμ| ≈ 20 D was found for the main absorption peak of spheroidenone (an acceptor substituted derivative of spheroidene) embedded in a nonpolar organic glass - an internal field effect. However, in this case the vibronic side bands clearly show some variation in their |Δμ| values. Even larger differences in the electrooptic response of different vibronic bands have been found for other acceptor substituted carotenoids where the acceptor group is very strong [Bublitz, G. U.; Boxer, S. G. Unpublished results].
59. Differences, however, do exist between internal electric field effects (such as those produced by the end groups) and external ones (such as those of the solvent matrix) with regard to the heterogeneity of the electrooptic parameters. This was demonstrated in a Stark spectroscopic study of the carotenoid derivative spheroidene which is one of the chromophores of the B800-850 antenna complex protein. [Gottfried, D. S.; Steffen, M. A.; Boxer, S. G. Biochim. Biophys. Acta 1991, 1059, 76-90 and Science 1991, 251, 662-665]. Embedded in a nonpolar organic glass spheroidene shows only moderately small values of |Δμ| < 4.7 D. However, for the same chromophore, now at its position inside the protein, this value changes dramatically and |Δμ| ≈ 15 D for the main absorption peak as well as for all vibronic side bands. This large |Δμ| is apparently due to the effect of the protein matrix on the electronic structure of the chromophore - effectively an external field effect. A comparably large value of |Δμ| ≈ 20 D was found for the main absorption peak of spheroidenone (an acceptor substituted derivative of spheroidene) embedded in a nonpolar organic glass - an internal field effect. However, in this case the vibronic side bands clearly show some variation in their |Δμ| values. Even larger differences in the electrooptic response of different vibronic bands have been found for other acceptor substituted carotenoids where the acceptor group is very strong [Bublitz, G. U.; Boxer, S. G. Unpublished results].
60. Differences, however, do exist between internal electric field effects (such as those produced by the end groups) and external ones (such as those of the solvent matrix) with regard to the heterogeneity of the electrooptic parameters. This was demonstrated in a Stark spectroscopic study of the carotenoid derivative spheroidene which is one of the chromophores of the B800-850 antenna complex protein. [Gottfried, D. S.; Steffen, M. A.; Boxer, S. G. Biochim. Biophys. Acta 1991, 1059, 76-90 and Science 1991, 251, 662-665]. Embedded in a nonpolar organic glass spheroidene shows only moderately small values of |Δμ| < 4.7 D. However, for the same chromophore, now at its position inside the protein, this value changes dramatically and |Δμ| ≈ 15 D for the main absorption peak as well as for all vibronic side bands. This large |Δμ| is apparently due to the effect of the protein matrix on the electronic structure of the chromophore - effectively an external field effect. A comparably large value of |Δμ| ≈ 20 D was found for the main absorption peak of spheroidenone (an acceptor substituted derivative of spheroidene) embedded in a nonpolar organic glass - an internal field effect. However, in this case the vibronic side bands clearly show some variation in their |Δμ| values. Even larger differences in the electrooptic response of different vibronic bands have been found for other acceptor substituted carotenoids where the acceptor group is very strong [Bublitz, G. U.; Boxer, S. G. Unpublished results].