The solvatochromic behaviour of 2- and 4-pyridiniophenoxides

González, Danilo; Neilands, O.; Rezende, Marcos Caroli

doi:10.1039/a900470j

Cited by 45 publications

(57 citation statements)

References 11 publications

(4 reference statements)

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“…Unfortunately, there seems to be little experimental evidence for S 1 -S 0 frequency variation as a result of conformational change. A comparison of Betaine 30 with sterically less encumbered betaine derivatives that are synthetically easily available [29] could be of great help in clarifying the role of central bond torsion on spectra.…”

Section: Discussionmentioning

confidence: 99%

Motional narrowing of broadband absorption of solvatochromic indicator Betaine 30

Renge

2009

Journal of Luminescence

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Section: Discussionmentioning

confidence: 99%

Motional narrowing of broadband absorption of solvatochromic indicator Betaine 30

Renge

2009

Journal of Luminescence

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“…The parent compounds are twisted by about 30°(C 2 symmetry) [74]. Whereas the parent thioxide 53a (X=O, R=H) is unknown, the oxide has recently been synthesized and measured spectroscopically [75]. Unfortunately, the parent pyridino N-phenoxide (53a, X=O, R=H) is not suf®ciently soluble in nonpolar solvents.…”

Section: Selected Chromophores and Bichromphoresmentioning

confidence: 98%

“…A TDDFT test calculation of the spiro [4,4]nonatetraene (75) with two weakly interacting pp* chromophores [87] led to a deviation twice as large than the mean average deviation (0.5 eV, cf. data in the footnote to Table 4).…”

Section: Selected Chromophores and Bichromphoresmentioning

confidence: 99%

Electronic excitation of sulfur-organic compounds - performance of time-dependent density functional theory

Fabian

2001

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

184

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To de®ne the scope and limitations of the time-dependent density functional theory (TDDFT) method, spectral absorption data of a series of about 100 neutral or charged sulfur-organic compounds with up to 24 non-hydrogen atoms and up to four sulfur atoms were calculated in the near-UV, visible and IR regions. Although the theoretical vertical transition energies correspond only approximately to experimental absorption band maxima, the mean absolute deviation was calculated to be 0.21 eV (1600 cm )1 ). The main absorption features of various compounds with monocoordinated or dicoordinated sulfur atoms are well reproduced. As far as possible TDDFT results were compared with those of semiempirical Zerner's intermediate neglect of dierential overlap (ZINDO/S) and of Pariser±Parr±Pople (PPP) calculations. TDDFT also works well in cases where the semiempirical methods fail. Limitations of TDDFT were encountered with calculations of spectral absorptions of dye molecules. The``vinylene shift'' of polymethine dyes is not reproduced by TDDFT. Whereas electronic excitation energies delocalized polar and betainic chromophores are reasonably well reproduced, excitation energies of charge-transfer-type and charge-resonance-type transitions of weakly interacting composite chromophores are signi®cantly underestimated.

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“…The experimental λ max values in water and toluene are, respectively, 378 and 529 nm. 8 The calculated solvatochromic shift for OB from water to toluene solvent is 7552 cm -1 . Consequently, the solvatochromic shift in water when compared to the gas phase of OB should be larger than 7552 cm -1 .…”

Section: Introductionmentioning

confidence: 99%

Role of Dynamic Flexibility in Computing Solvatochromic Properties of Dye−Solvent Systems: o-Betaine in Water

Murugan

Ågren

2009

J. Phys. Chem. A

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Car-Parrinello molecular dynamics (CPMD) and Car-Parrinello mixed quantum mechanics/classical mechanics (CP-QM/MM) calculations were performed for o-betaine (OB) in the gas phase and water as solvent to study the solvent dependence on its molecular properties: geometry, charge distribution, and dipole moment. It is found that the molecular geometry in the gas phase is close to the planar structure, while in the water it is a twisted structure. The calculations clearly show that in both the gas phase and water the OB molecule is highly flexible with a large amplitude for the twist angle motion. The average gas-phase dipole moment for OB doubles in water, something that concords with a strong increase of total charge on phenoxide and pyridinium rings. We also investigated the solvatochromic shift in the pi-pi* and n-pi* transitions by carrying out INDO/CIS calculations for the gas-phase and solution-phase configurations obtained from the CPMD and CP-QM/MM calculations with results that are in good agreement with available experimental values (J. Chem. Soc., Perkin Trans. 2 1999, 1, 713). Our work indicates the importance of allowing full structural and dynamic flexibility of dye-solvent systems in predicting their basic solvatochromic properties.

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The solvatochromic behaviour of 2- and 4-pyridiniophenoxides

Cited by 45 publications

References 11 publications

Motional narrowing of broadband absorption of solvatochromic indicator Betaine 30

Motional narrowing of broadband absorption of solvatochromic indicator Betaine 30

Electronic excitation of sulfur-organic compounds - performance of time-dependent density functional theory

Role of Dynamic Flexibility in Computing Solvatochromic Properties of Dye−Solvent Systems: o-Betaine in Water

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