Internal conversion with 4-(azetidinyl)benzonitriles in alkane solvents. Influence of fluoro substitution

S. I. Druzhinin, Y. B. Jiang, A. Demeter, K. A. Zachariasse

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The introduction of a fluoro-substituent in the phenyl ring of 4-(1-azetidinyl)benzonitrile (P4C) leads to smaller fluorescence quantum yields Φf and shorter decay times τ in alkane solvents (cyclopentane, n-hexadecane, n-hexane and 2-methylpentane). In cyclopentane at 25°C, Φf and τ equal 0.02 and 0.14 ns for 2-fluoro-4-(1-azetidinyl)benzonitrile (P4CF2) and 0.11 and 0.85 ns for 3-fluoro-4-(1-azetidinyl)benzonitrile (P4CF3), as compared with 0.27 and 4.55 ns for P4C. The fluorescence originates from a locally excited (LE) state and dual fluorescence due to intramolecular charge transfer is not observed for the three aminobenzonitriles at any temperature in the alkane solvents. By measuring the yields of intersystem crossing ΦISC, it follows that this enhancement of the radiationless deactivation of the first excited singlet state S1 is due to thermally activated internal conversion (IC). The IC yield ΦIC in cyclopentane at 25°C, as an example, is considerably larger for P4CF2 (0.93) than for P4CF3 (0.35) and of minor importance for P4C (0.03). The IC activation energies EIC of P4CF2 (12.6 kJ mol-1), P4CF3 (19.3 kJ mol-1) and P4C (38.1 kJ mol-1) in cyclopentane were determined by fitting τ measured as a function of temperature, together with data for Φf and ΦISC . Similar EIC values were obtained in n-hexane and n-hexadecane. These data show that the increase in IC efficiency from P4C via P4CF3 to P4CF2 is caused by a decrease in EIC. The radiative rate constants kf in cyclopentane of P4CF2 and P4CF3 are about twice that of P4C, probably due to the mixing of the S2(1La, CT) and S1(1Lb) states of P4C caused by the molecular asymmetry introduced by the F-substituents. It is assumed that the lowering of the IC barriers in P4CF2 and P4CF3 is governed by an F-substituent-dependent difference in the energies of the molecular configuration of the azetidinylbenzonitriles that can be reached in S1 as compared with those in S0.

Original languageEnglish
Pages (from-to)5213-5221
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume3
Issue number23
DOIs
Publication statusPublished - 2001

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Cyclopentanes
Alkanes
internal conversion
alkanes
Substitution reactions
substitutes
Fluorescence
Excited states
fluorescence
Quantum yield
Conversion efficiency
Charge transfer
Rate constants
deactivation
Activation energy
excitation
benzonitrile
Temperature
charge transfer
asymmetry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Internal conversion with 4-(azetidinyl)benzonitriles in alkane solvents. Influence of fluoro substitution. / Druzhinin, S. I.; Jiang, Y. B.; Demeter, A.; Zachariasse, K. A.

In: Physical Chemistry Chemical Physics, Vol. 3, No. 23, 2001, p. 5213-5221.

Research output: Contribution to journalArticle

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abstract = "The introduction of a fluoro-substituent in the phenyl ring of 4-(1-azetidinyl)benzonitrile (P4C) leads to smaller fluorescence quantum yields Φf and shorter decay times τ in alkane solvents (cyclopentane, n-hexadecane, n-hexane and 2-methylpentane). In cyclopentane at 25°C, Φf and τ equal 0.02 and 0.14 ns for 2-fluoro-4-(1-azetidinyl)benzonitrile (P4CF2) and 0.11 and 0.85 ns for 3-fluoro-4-(1-azetidinyl)benzonitrile (P4CF3), as compared with 0.27 and 4.55 ns for P4C. The fluorescence originates from a locally excited (LE) state and dual fluorescence due to intramolecular charge transfer is not observed for the three aminobenzonitriles at any temperature in the alkane solvents. By measuring the yields of intersystem crossing ΦISC, it follows that this enhancement of the radiationless deactivation of the first excited singlet state S1 is due to thermally activated internal conversion (IC). The IC yield ΦIC in cyclopentane at 25°C, as an example, is considerably larger for P4CF2 (0.93) than for P4CF3 (0.35) and of minor importance for P4C (0.03). The IC activation energies EIC of P4CF2 (12.6 kJ mol-1), P4CF3 (19.3 kJ mol-1) and P4C (38.1 kJ mol-1) in cyclopentane were determined by fitting τ measured as a function of temperature, together with data for Φf and ΦISC . Similar EIC values were obtained in n-hexane and n-hexadecane. These data show that the increase in IC efficiency from P4C via P4CF3 to P4CF2 is caused by a decrease in EIC. The radiative rate constants kf in cyclopentane of P4CF2 and P4CF3 are about twice that of P4C, probably due to the mixing of the S2(1La, CT) and S1(1Lb) states of P4C caused by the molecular asymmetry introduced by the F-substituents. It is assumed that the lowering of the IC barriers in P4CF2 and P4CF3 is governed by an F-substituent-dependent difference in the energies of the molecular configuration of the azetidinylbenzonitriles that can be reached in S1 as compared with those in S0.",
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N2 - The introduction of a fluoro-substituent in the phenyl ring of 4-(1-azetidinyl)benzonitrile (P4C) leads to smaller fluorescence quantum yields Φf and shorter decay times τ in alkane solvents (cyclopentane, n-hexadecane, n-hexane and 2-methylpentane). In cyclopentane at 25°C, Φf and τ equal 0.02 and 0.14 ns for 2-fluoro-4-(1-azetidinyl)benzonitrile (P4CF2) and 0.11 and 0.85 ns for 3-fluoro-4-(1-azetidinyl)benzonitrile (P4CF3), as compared with 0.27 and 4.55 ns for P4C. The fluorescence originates from a locally excited (LE) state and dual fluorescence due to intramolecular charge transfer is not observed for the three aminobenzonitriles at any temperature in the alkane solvents. By measuring the yields of intersystem crossing ΦISC, it follows that this enhancement of the radiationless deactivation of the first excited singlet state S1 is due to thermally activated internal conversion (IC). The IC yield ΦIC in cyclopentane at 25°C, as an example, is considerably larger for P4CF2 (0.93) than for P4CF3 (0.35) and of minor importance for P4C (0.03). The IC activation energies EIC of P4CF2 (12.6 kJ mol-1), P4CF3 (19.3 kJ mol-1) and P4C (38.1 kJ mol-1) in cyclopentane were determined by fitting τ measured as a function of temperature, together with data for Φf and ΦISC . Similar EIC values were obtained in n-hexane and n-hexadecane. These data show that the increase in IC efficiency from P4C via P4CF3 to P4CF2 is caused by a decrease in EIC. The radiative rate constants kf in cyclopentane of P4CF2 and P4CF3 are about twice that of P4C, probably due to the mixing of the S2(1La, CT) and S1(1Lb) states of P4C caused by the molecular asymmetry introduced by the F-substituents. It is assumed that the lowering of the IC barriers in P4CF2 and P4CF3 is governed by an F-substituent-dependent difference in the energies of the molecular configuration of the azetidinylbenzonitriles that can be reached in S1 as compared with those in S0.

AB - The introduction of a fluoro-substituent in the phenyl ring of 4-(1-azetidinyl)benzonitrile (P4C) leads to smaller fluorescence quantum yields Φf and shorter decay times τ in alkane solvents (cyclopentane, n-hexadecane, n-hexane and 2-methylpentane). In cyclopentane at 25°C, Φf and τ equal 0.02 and 0.14 ns for 2-fluoro-4-(1-azetidinyl)benzonitrile (P4CF2) and 0.11 and 0.85 ns for 3-fluoro-4-(1-azetidinyl)benzonitrile (P4CF3), as compared with 0.27 and 4.55 ns for P4C. The fluorescence originates from a locally excited (LE) state and dual fluorescence due to intramolecular charge transfer is not observed for the three aminobenzonitriles at any temperature in the alkane solvents. By measuring the yields of intersystem crossing ΦISC, it follows that this enhancement of the radiationless deactivation of the first excited singlet state S1 is due to thermally activated internal conversion (IC). The IC yield ΦIC in cyclopentane at 25°C, as an example, is considerably larger for P4CF2 (0.93) than for P4CF3 (0.35) and of minor importance for P4C (0.03). The IC activation energies EIC of P4CF2 (12.6 kJ mol-1), P4CF3 (19.3 kJ mol-1) and P4C (38.1 kJ mol-1) in cyclopentane were determined by fitting τ measured as a function of temperature, together with data for Φf and ΦISC . Similar EIC values were obtained in n-hexane and n-hexadecane. These data show that the increase in IC efficiency from P4C via P4CF3 to P4CF2 is caused by a decrease in EIC. The radiative rate constants kf in cyclopentane of P4CF2 and P4CF3 are about twice that of P4C, probably due to the mixing of the S2(1La, CT) and S1(1Lb) states of P4C caused by the molecular asymmetry introduced by the F-substituents. It is assumed that the lowering of the IC barriers in P4CF2 and P4CF3 is governed by an F-substituent-dependent difference in the energies of the molecular configuration of the azetidinylbenzonitriles that can be reached in S1 as compared with those in S0.

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