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Effect of environment on pressure-induced emission of benzophenone, 4,4{prime}-dichlorobenzophenone, and 4-(dimethylamino)benzaldehyde in solid media

Journal Article · · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
DOI:https://doi.org/10.1021/jp962801n· OSTI ID:505198
;  [1]
  1. Univ. of Illinois, Urbana, IL (United States)

The pressure-induced emission of three aromatic carbonyls - benzophenone (BP), 4,4{prime}-dichlorobenzophenone (DCBP), and 4-(dimethylamino)benzaldehyde (DMABA) - dissolved in solid polymers and also in their crystalline state has been studied. Under pressure all compounds dissolved in polymers reveal a significant enhancement of the luminescence emission in the low-pressure region. The degree of increase is strongly dependent on the type of polymer. DMABA exhibits both fluorescence and phosphorescence, whereas BP and DCBP molecules show only phosphorescence. For all these molecules a model based on the increase with increasing pressure of the amount of {pi},{pi}{sup *} character in the initially predominately n,{pi}{sup *} triplet state is proposed to account for the observed increase of the emission intensity. In the case of DMABA it is proposed that the increase of the {pi},{pi}{sup *} character in the triplet state increases the emission intensity in two concurrent steps: by an increase of the radiative rate from the triplet state and by a decrease of the intersystem crossing rate between singlet and triplet states. The first factor increases phosphorescence intensity, and the second one effects the fluorescence. In the case of BP and DCBP, where the intersystem crossing process is very fast, the increase of pressure increases mainly the radiative rate of the lowest triplet state. 22 refs., 8 figs.

OSTI ID:
505198
Journal Information:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 8 Vol. 101; ISSN 1089-5639; ISSN JPCAFH
Country of Publication:
United States
Language:
English