Twist conformational effects on the excited triplet states of aromatic ketones studied by multifrequency TREPR and pulsed EPR spectroscopy

T. Ikoma, K. Akiyama, S. Tero-Kubota

研究成果: Article査読

7 被引用数 (Scopus)

抄録

Employing X- and Q-band time-resolved EPR and pulsed EPR techniques, we have investigated effects of twist conformation on the electronic structures and magnetic properties of the lowest excited triplet states of alkyl phenyl ketones. The conformational variation due to steric hindrance of a bulky substituent on the α-position drastically leads to a decrease of the zerofield splitting constant of D and an increase of the energy gap between 3nπ* and 3ππ* states. Hydrogen bonding with H2O destabilized significantly the 3nπ* state and switched the T1 state to the 3ππ* state. t-Butyl phenyl ketone gave unusually broad EPR spectra in rigid glassy matrices. The multifrequency and pulsed EPR measurements clarified that the inhomogeneously broadening spectra were ascribable to the distribution of the dihedral angle about a twist conformation. Asymmetric distribution of the ZFS parameters was interpreted in terms of the perturbation of spin—orbit interactions to the spin sublevels.

本文言語English
ページ(範囲)813-820
ページ数8
ジャーナルMolecular Physics
96
5
DOI
出版ステータスPublished - 1999 3

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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