| 1. |
- Ruseckas, Arvydas, et al.
(författare)
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Conformations and Photophysics of a Stilbene Dimer.
- 2003
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Ingår i: The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. - : American Chemical Society (ACS). - 1520-5215. ; 107:40, s. 8029-8034
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Tidskriftsartikel (refereegranskat)abstract
- Photophysical studies of pseudo-p-distyryl[2.2]paracyclophane, a model molecule of a stilbene dimer arranged in a brick-wall geometry, in tetrahydrofurane solution indicate the existence of at least two conformers in the ground state. The conformer A with the smallest optical gap of 3 eV has a short radiative lifetime of 3.3 ns, while the conformer B with an optical gap about 0.3 eV larger is much more abundant in solution and its radiative lifetime is about 10 times longer. Ab initio calculations show that the ground-state energy has a shallow minimum with respect to the torsional angle between the styryl side group and the paracyclophane core around the zero position, with the lowest energy conformation at a torsional angle of -21. On this basis, A and B are assigned to flat and twisted conformations, respectively. Conformer B shows a partial decay of excited-state absorption and fluorescence with a time constant ranging from 5 to 30 ps, depending on excitation photon energy. We attribute this to isomerization of the stilbene moiety, which initially keeps conjugation in the ground state. The isomerization product is long-lived and tends to accumulate in solution.
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| 2. |
- Ruseckas, Arvydas, et al.
(författare)
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Luminescence quenching by inter-chain aggregates in substituted polythiophenes
- 2001
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Ingår i: Journal of Photochemistry and Photobiology, A: Chemistry. - 1873-2666 .- 1010-6030. ; 144:1, s. 3-12
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Tidskriftsartikel (refereegranskat)abstract
- Time-resolved photo luminescence spectra measured in solid films of two polythiophene derivatives with different chain packing allow to distinguish emission of intra-chain excitations from the luminescence of inter-chain aggregates. Aggregate luminescence is red shifted by about 0.1 eV relative to intra-chain emission and shows vibronic coupling to the C=C bond stretch with the Huang-Phys factor of S approximate to 1.5, which is twice bigger than that of the intra-chain emission. Combining time resolved luminescence data with femtosecond transient absorption, we show that the dynamic quenching of the luminescence in films with dense chain packing is mainly due to excitation energy transfer to aggregates. The radiative lifetime of the lowest excited state of the aggregate with the optical gap of 1.84-1.9 eV is estimated to be about 20 ns. The aggregate contribution to the total luminescence in the polythiophene films with dense chain packing is about 50% and does not change significantly with temperature. (C) 2001 Elsevier Science B.V. All rights reserved.
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