Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Photophysical Behaviors of Biphenylcarboxylic Acids in Various Solvents; Excited-State Geometry Change and Intramolecular Charge Transfer

  • Yoon Minjoong (Department of Chemistry, Chungnam National University) ;
  • Cho Dae Won (Department of Chemistry, Chungnam National University) ;
  • Lee Jae Young (Department of Chemistry, Chungnam National University)
  • Published : 1992.12.20
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Abstract

The solvent-dependent photophysical properties of 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid(4BPCA), which have a pre-twisted conformation in the ground state, have been investigated. The fluorescence spectra of 4BPCA show vibrational structure with a non-mirror image to the absorption spectra in nonpolar solvent while those of 2BPCA show no structure even in nonpolar solvents. As the solvent polarity increases, the fluorescence spectra become diffuse and broad with a strong red shift resulting in the large Stokes shift. The large fluorescence Stokes shift of BPCA's in polar solvent is also partially due to an intramolecular charge transfer (ICT) interaction in the excited state, as demonstrated by the large dipole moment in the excited state (7.6-10.6 D). The fluorescence decay behaviors of BPCA's (decay-times and their pre-exponential factors) also depend on solvent polarity in agreement with the solvent-dependent properties of the steady-state fluorecence. The data have been discussed in terms of change in the excited-state potential energy surface with respect to change of the dihedral angle of biphenyl moiety.

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