Charged push - Pull polyenes in solution: Anomalous solvatochromism and nonlinear optical properties

Journal of Physical Chemistry A

Volumn 107, Issue 31, 2003, Pages 6032-6046

  Laage, Damien ^a   Thompson, Ward H ^b   Blanchard Desce, Mireille ^c   Hynes, James T ^a,d  

^a ECOLE NORMALE SUPÉRIEURE   (France)

^b UNIVERSITY OF KANSAS   (United States)

^c UNIVERSITÉ DE RENNES 1   (France)

^d UNIVERSITY OF COLORADO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER; IMAGING TECHNIQUES; NONLINEAR OPTICS; OPTICAL PROPERTIES; SECOND HARMONIC GENERATION; SOLVENTS;

SOLVATOCHROMISM;

POLYOLEFINS;

EID: 0042733482     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0276597     Document Type: Article

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54. 42 thus, the only observed fluorescence is emitted from the same excited state as the Franck-Condon state reached by absorption.
55. 42 thus, the only observed fluorescence is emitted from the same excited state as the Franck-Condon state reached by absorption.
56. 42 thus, the only observed fluorescence is emitted from the same excited state as the Franck-Condon state reached by absorption.
57. 42 thus, the only observed fluorescence is emitted from the same excited state as the Franck-Condon state reached by absorption.
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60. Bayliss, N. S.; McRae, E. G. J. Phys. Chem. 1954, 58, 1002-1006. McRae, E. G. J. Phys. Chem. 1957, 61, 562-572. McRae, E. G. Spectrochim. Acta 1958, 12, 192-210. Lippert, E. Z. Elektrochem. 1961, 61, 962. Liptay, W. Z. Naturforsch. 1965, 20a, 1441-1471. Liptay, W.; Walz, G. Z. Naturforsch. 1971, 26a, 2007-2019.
61. Bayliss, N. S.; McRae, E. G. J. Phys. Chem. 1954, 58, 1002-1006. McRae, E. G. J. Phys. Chem. 1957, 61, 562-572. McRae, E. G. Spectrochim. Acta 1958, 12, 192-210. Lippert, E. Z. Elektrochem. 1961, 61, 962. Liptay, W. Z. Naturforsch. 1965, 20a, 1441-1471. Liptay, W.; Walz, G. Z. Naturforsch. 1971, 26a, 2007-2019.
62. Bayliss, N. S.; McRae, E. G. J. Phys. Chem. 1954, 58, 1002-1006. McRae, E. G. J. Phys. Chem. 1957, 61, 562-572. McRae, E. G. Spectrochim. Acta 1958, 12, 192-210. Lippert, E. Z. Elektrochem. 1961, 61, 962. Liptay, W. Z. Naturforsch. 1965, 20a, 1441-1471. Liptay, W.; Walz, G. Z. Naturforsch. 1971, 26a, 2007-2019.
63. Bayliss, N. S.; McRae, E. G. J. Phys. Chem. 1954, 58, 1002-1006. McRae, E. G. J. Phys. Chem. 1957, 61, 562-572. McRae, E. G. Spectrochim. Acta 1958, 12, 192-210. Lippert, E. Z. Elektrochem. 1961, 61, 962. Liptay, W. Z. Naturforsch. 1965, 20a, 1441-1471. Liptay, W.; Walz, G. Z. Naturforsch. 1971, 26a, 2007-2019.
64. Bayliss, N. S.; McRae, E. G. J. Phys. Chem. 1954, 58, 1002-1006. McRae, E. G. J. Phys. Chem. 1957, 61, 562-572. McRae, E. G. Spectrochim. Acta 1958, 12, 192-210. Lippert, E. Z. Elektrochem. 1961, 61, 962. Liptay, W. Z. Naturforsch. 1965, 20a, 1441-1471. Liptay, W.; Walz, G. Z. Naturforsch. 1971, 26a, 2007-2019.
65. The Kosower Z-value polarity scale (Kosower, E. M. J. Am. Chem. Soc. 1958, 80, 3253-3260) is based on the solvatochromic behavior of 1-ethyl-4-(carbomethoxy)pyridinium iodide. This salt forms a tight ion-pair complex in solution. While in CPPP the absorption transition corresponds to an intramolecular CT not involving the counterion, the excitation of pyridinium iodide induces an electron transfer (ET) from the iodide anion to the pyridinium ring, resulting in two radicals. Kosower explains the observed blue shift in absorption with increasing solvent polarity by the smaller dipole moment of the excited state compared to the ground state. The details of this explanation have been contested (Larsen, J. W.; Edwards, A. G.; Dobi, P. J. Am. Chem. Soc. 1980, 102, 6780-6783), but the ET from the iodide anion to the pyridinium ring seems well established because the two resulting radicals have been experimentally detected after excitation (Kosower, E. M.; Lindqvist, L. Tetrahedron Lett. 1965, 50, 4481-4485). The absorption blue shifts observed for CPPP and pyridinium iodide have qualitatively different origins because for pyridinium iodide it is an equilibrium solvation effect and a blue shift should be observed in emission as well while for CPPP it is a purely nonequilibrium effect and absorption and emission wavelengths shift in opposite directions.
66. The Kosower Z-value polarity scale (Kosower, E. M. J. Am. Chem. Soc. 1958, 80, 3253-3260) is based on the solvatochromic behavior of 1-ethyl-4-(carbomethoxy)pyridinium iodide. This salt forms a tight ion-pair complex in solution. While in CPPP the absorption transition corresponds to an intramolecular CT not involving the counterion, the excitation of pyridinium iodide induces an electron transfer (ET) from the iodide anion to the pyridinium ring, resulting in two radicals. Kosower explains the observed blue shift in absorption with increasing solvent polarity by the smaller dipole moment of the excited state compared to the ground state. The details of this explanation have been contested (Larsen, J. W.; Edwards, A. G.; Dobi, P. J. Am. Chem. Soc. 1980, 102, 6780-6783), but the ET from the iodide anion to the pyridinium ring seems well established because the two resulting radicals have been experimentally detected after excitation (Kosower, E. M.; Lindqvist, L. Tetrahedron Lett. 1965, 50, 4481-4485). The absorption blue shifts observed for CPPP and pyridinium iodide have qualitatively different origins because for pyridinium iodide it is an equilibrium solvation effect and a blue shift should be observed in emission as well while for CPPP it is a purely nonequilibrium effect and absorption and emission wavelengths shift in opposite directions.
67. The Kosower Z-value polarity scale (Kosower, E. M. J. Am. Chem. Soc. 1958, 80, 3253-3260) is based on the solvatochromic behavior of 1-ethyl-4-(carbomethoxy)pyridinium iodide. This salt forms a tight ion-pair complex in solution. While in CPPP the absorption transition corresponds to an intramolecular CT not involving the counterion, the excitation of pyridinium iodide induces an electron transfer (ET) from the iodide anion to the pyridinium ring, resulting in two radicals. Kosower explains the observed blue shift in absorption with increasing solvent polarity by the smaller dipole moment of the excited state compared to the ground state. The details of this explanation have been contested (Larsen, J. W.; Edwards, A. G.; Dobi, P. J. Am. Chem. Soc. 1980, 102, 6780-6783), but the ET from the iodide anion to the pyridinium ring seems well established because the two resulting radicals have been experimentally detected after excitation (Kosower, E. M.; Lindqvist, L. Tetrahedron Lett. 1965, 50, 4481-4485). The absorption blue shifts observed for CPPP and pyridinium iodide have qualitatively different origins because for pyridinium iodide it is an equilibrium solvation effect and a blue shift should be observed in emission as well while for CPPP it is a purely nonequilibrium effect and absorption and emission wavelengths shift in opposite directions.
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