Conformations and Photophysics of a Stilbene Dimer.
(2003) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 107(40). p.8029-8034- 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... (More)
- 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. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/128205
- author
- Ruseckas, Arvydas ; Namdas, Ebinazar B ; Lee, J Y ; Mukamel, S ; Wang, S J ; Bazan, G C and Sundström, Villy LU
- organization
- publishing date
- 2003
- type
- Contribution to journal
- publication status
- published
- subject
- in
- The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
- volume
- 107
- issue
- 40
- pages
- 8029 - 8034
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000185757100004
- scopus:0242270985
- ISSN
- 1520-5215
- DOI
- 10.1021/jp027536m
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- 0b993f16-8cef-4363-aecc-42e673b3293e (old id 128205)
- date added to LUP
- 2016-04-01 15:38:50
- date last changed
- 2022-03-22 05:28:17
@article{0b993f16-8cef-4363-aecc-42e673b3293e,
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.}},
author = {{Ruseckas, Arvydas and Namdas, Ebinazar B and Lee, J Y and Mukamel, S and Wang, S J and Bazan, G C and Sundström, Villy}},
issn = {{1520-5215}},
language = {{eng}},
number = {{40}},
pages = {{8029--8034}},
publisher = {{The American Chemical Society (ACS)}},
series = {{The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory}},
title = {{Conformations and Photophysics of a Stilbene Dimer.}},
url = {{http://dx.doi.org/10.1021/jp027536m}},
doi = {{10.1021/jp027536m}},
volume = {{107}},
year = {{2003}},
}