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Volumn 9, Issue 9, 2003, Pages 1991-2007

A distinctive example of the cooperative interplay of structure and environment in tuning of intramolecular charge transfer in second-order nonlinear optical chromophores

Author keywords

Ab initio calculations; Annelation; Heterocyclic zwitterions; NMR spectroscopy; Nonlinear optics

Indexed keywords

ALKYLATION; CHARGE TRANSFER; DYES; NEGATIVE IONS; NONLINEAR OPTICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS (CHEMICAL); ULTRAVIOLET SPECTROSCOPY;

EID: 0038814054     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200204356     Document Type: Article
Times cited : (170)

References (87)
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    • A preliminary investigation into the concentration-dependent UV/Vis absorption of 1b and 2b in dioxane has shown that the normalized absorption of the lowest energy band increases with decreasing concentration, while that of the highest energy band decreases correspondingly, supporting the hypothesis that the former band could be attributable to the monomeric species. A vibronic structure of the spectra at higher dilution was also observed. A detailed UV/Vis, NMR and computational investigation into aggregates is under way and will be reported in due course.
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    • 2-carbon atom, and have subsequently used charge demands as a measure of the capacity of group X to delocalize positive or negative charge: a) S. Bradamante, G. A. Pagani, J. Chem. Soc. Perkin Trans. 2 1986, 1035-1045; b) S. Bradamante, G. A. Pagani, Pure Appl. Chem. 1989, 61, 709-716; c) E. Barchiesi, S. Bradamante, R. Ferraccioli, G. A. Pagani, J. Chem. Soc. Perkin Trans. 2 1990, 375-383.
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    • Bradamante, S.1    Pagani, G.A.2
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    • 2-carbon atom, and have subsequently used charge demands as a measure of the capacity of group X to delocalize positive or negative charge: a) S. Bradamante, G. A. Pagani, J. Chem. Soc. Perkin Trans. 2 1986, 1035-1045; b) S. Bradamante, G. A. Pagani, Pure Appl. Chem. 1989, 61, 709-716; c) E. Barchiesi, S. Bradamante, R. Ferraccioli, G. A. Pagani, J. Chem. Soc. Perkin Trans. 2 1990, 375-383.
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    • Bradamante, S.1    Pagani, G.A.2
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    • 2-carbon atom, and have subsequently used charge demands as a measure of the capacity of group X to delocalize positive or negative charge: a) S. Bradamante, G. A. Pagani, J. Chem. Soc. Perkin Trans. 2 1986, 1035-1045; b) S. Bradamante, G. A. Pagani, Pure Appl. Chem. 1989, 61, 709-716; c) E. Barchiesi, S. Bradamante, R. Ferraccioli, G. A. Pagani, J. Chem. Soc. Perkin Trans. 2 1990, 375-383.
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    • Barchiesi, E.1    Bradamante, S.2    Ferraccioli, R.3    Pagani, G.A.4
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    • a) F. Würthner, R. Wortmann, R. Matschiner, K. Lukaszuk, K. Meerholz, Y. DeNardin, R. Bittner, C. Bräuchle, R. Sens, Angew. Chem. 1997, 109, 2933-2936; Angew. Chem. Int. Ed. Engl. 1997, 36, 2765-2768;
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    • note
    • Computations were partially carried out at the Cineca Supercomputer Center in Bologna (Italy) on SGI Origin 3800 and IBM SP RS/6000 Power3 machines.
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    • note
    • 3 and DMF. DFT-computed dipole moment values are included in Table 4.
  • 71
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    • We are aware that the Onsager reaction field model should be used only under the strict assumption that all chromophores are spherical in shape, a case clearly not applicable here. Recent work by Dalton and Robinson on a Monte Carlo treatment of the electrooptic activity of dipolar chromophores has indeed pointed out the effect of spherical versus ellipsoidal shapes, the latter fitting experimental data more closely (B. H. Robinson, L. R. Dalton, J. Phys. Chem. 2000, 104, 4785-4795). Unfortunately, other theoretical models available in the Gaussian package, such as the polarized continuum model (PCM), in which the cavity is defined as the sum of a series of interlocking spheres, or the alternative self-consistent isodensity polarized continuum model (SCI-PCM), did not satisfy convergence criteria during geometry optimizations even of the smallest system 1c. It became evident that the Onsager model was the only method able to satisfy convergence criteria completely for the full set of compounds and solvents to be considered in this study. Such a simplification could be responsible for a certain degree of deviation from experimental data. However, we believe that the overall good, and sometimes very good, agreement with different experimental data do validate this computational approach.
    • (2000) J. Phys. Chem. , vol.104 , pp. 4785-4795
    • Robinson, B.H.1    Dalton, L.R.2
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    • note
    • 1 structure is not significant.
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    • As Incorporated in the GAUSSIAN 98 Package
    • Gaussian NBO. Version 3.1 (as incorporated in the GAUSSIAN 98 package).
    • Gaussian NBO. Version 3.1
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    • (Eds.: D.L. Wise, G.E. Wnek, D.J. Trantolo, T.M. Cooper, J.D. Gresser), Marcel Dekker, New York
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.