Effects of molecular structure and hydrogen bonding on the radiationless deactivation of singlet excited fluorenone derivatives

L. Biczók, T. Bérces, Haruo Inoue

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Abstract

Substituent effects on intramolecular radiationless deactivation and hydrogen-bonding-induced quenching have been examined for various fluorenone derivatives. In toluene, triplet formation is the dominant process from the singlet excited state when an electron-withdrawing group is attached to the fluorenone moiety, whereas an electron-donating substituent promotes internal conversion. There is a clear correlation between the internal conversion rate constant and the lowest excited singlet state energy, which can be explained in terms of the energy gap law. It is shown that both the electron-donating character of the substituent in the excited fluorenone and the hydrogen-bonding power of alcohol play important roles in determining the rate of dynamic quenching by alcohols. The intermolecular hydrogen bonding with alcohols in the singlet excited state acts as an effective accepting mode of radiationless deactivation for fluorenones substituted with an electron-donating group. However, 2-NO2-and 2-COOCH3-derivatives are poorly quenched by alcohols. The parallel change of the hydrogen-bonding-induced quenching rate constants and the dipole moment difference between the ground and the singlet excited states suggests that the electron density around the carbonyl oxygen controls the quenching rate in the series of 2-substituted fluorenones.

Original languageEnglish
Pages (from-to)3837-3842
Number of pages6
JournalJournal of Physical Chemistry A
Volume103
Issue number20
Publication statusPublished - May 20 1999

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Excited states
deactivation
Molecular structure
Quenching
Hydrogen bonds
alcohols
molecular structure
quenching
Alcohols
Derivatives
Electrons
internal conversion
hydrogen
excitation
Rate constants
electrons
Dipole moment
Toluene
Carrier concentration
toluene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Substituent effects on intramolecular radiationless deactivation and hydrogen-bonding-induced quenching have been examined for various fluorenone derivatives. In toluene, triplet formation is the dominant process from the singlet excited state when an electron-withdrawing group is attached to the fluorenone moiety, whereas an electron-donating substituent promotes internal conversion. There is a clear correlation between the internal conversion rate constant and the lowest excited singlet state energy, which can be explained in terms of the energy gap law. It is shown that both the electron-donating character of the substituent in the excited fluorenone and the hydrogen-bonding power of alcohol play important roles in determining the rate of dynamic quenching by alcohols. The intermolecular hydrogen bonding with alcohols in the singlet excited state acts as an effective accepting mode of radiationless deactivation for fluorenones substituted with an electron-donating group. However, 2-NO2-and 2-COOCH3-derivatives are poorly quenched by alcohols. The parallel change of the hydrogen-bonding-induced quenching rate constants and the dipole moment difference between the ground and the singlet excited states suggests that the electron density around the carbonyl oxygen controls the quenching rate in the series of 2-substituted fluorenones.",
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AU - Bérces, T.

AU - Inoue, Haruo

PY - 1999/5/20

Y1 - 1999/5/20

N2 - Substituent effects on intramolecular radiationless deactivation and hydrogen-bonding-induced quenching have been examined for various fluorenone derivatives. In toluene, triplet formation is the dominant process from the singlet excited state when an electron-withdrawing group is attached to the fluorenone moiety, whereas an electron-donating substituent promotes internal conversion. There is a clear correlation between the internal conversion rate constant and the lowest excited singlet state energy, which can be explained in terms of the energy gap law. It is shown that both the electron-donating character of the substituent in the excited fluorenone and the hydrogen-bonding power of alcohol play important roles in determining the rate of dynamic quenching by alcohols. The intermolecular hydrogen bonding with alcohols in the singlet excited state acts as an effective accepting mode of radiationless deactivation for fluorenones substituted with an electron-donating group. However, 2-NO2-and 2-COOCH3-derivatives are poorly quenched by alcohols. The parallel change of the hydrogen-bonding-induced quenching rate constants and the dipole moment difference between the ground and the singlet excited states suggests that the electron density around the carbonyl oxygen controls the quenching rate in the series of 2-substituted fluorenones.

AB - Substituent effects on intramolecular radiationless deactivation and hydrogen-bonding-induced quenching have been examined for various fluorenone derivatives. In toluene, triplet formation is the dominant process from the singlet excited state when an electron-withdrawing group is attached to the fluorenone moiety, whereas an electron-donating substituent promotes internal conversion. There is a clear correlation between the internal conversion rate constant and the lowest excited singlet state energy, which can be explained in terms of the energy gap law. It is shown that both the electron-donating character of the substituent in the excited fluorenone and the hydrogen-bonding power of alcohol play important roles in determining the rate of dynamic quenching by alcohols. The intermolecular hydrogen bonding with alcohols in the singlet excited state acts as an effective accepting mode of radiationless deactivation for fluorenones substituted with an electron-donating group. However, 2-NO2-and 2-COOCH3-derivatives are poorly quenched by alcohols. The parallel change of the hydrogen-bonding-induced quenching rate constants and the dipole moment difference between the ground and the singlet excited states suggests that the electron density around the carbonyl oxygen controls the quenching rate in the series of 2-substituted fluorenones.

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