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Temperature-Dependent Exciton Dynamics in J-Aggregates-When Disorder Plays a Role.

Kaiser, Theo E; Scheblykin, Ivan LU ; Thomsson, Daniel LU and Würthner, Frank (2009) In The Journal of Physical Chemistry Part B 113. p.15836-15842
Abstract
Absorption and fluorescence spectral properties of J-aggregates of core-tetrasubstituted perylene bisimide (PBI) dyes have been investigated in the temperature range from 300 to 5 K. A special feature of the present PBI J-aggregates is that, in contrast to classical J-aggregates like that of pseudoisocyanine (PIC), the chromophores are held together not only by van-der-Waals interactions but also by hydrogen bonds. The temperature dependence of the spectral band widths and the Stokes shift for PBI 1 aggregates are compared with those for 3,3'-bis-(3-sulfopropyl)-5,5'-dichloro-9-ethylthiacarbocyanine (THIATS) J-aggregates, which have been studied in detail previously (J. Phys. Chem. B 2001, 105, 4636-4646). The assemblies of PBI 1 possess... (More)
Absorption and fluorescence spectral properties of J-aggregates of core-tetrasubstituted perylene bisimide (PBI) dyes have been investigated in the temperature range from 300 to 5 K. A special feature of the present PBI J-aggregates is that, in contrast to classical J-aggregates like that of pseudoisocyanine (PIC), the chromophores are held together not only by van-der-Waals interactions but also by hydrogen bonds. The temperature dependence of the spectral band widths and the Stokes shift for PBI 1 aggregates are compared with those for 3,3'-bis-(3-sulfopropyl)-5,5'-dichloro-9-ethylthiacarbocyanine (THIATS) J-aggregates, which have been studied in detail previously (J. Phys. Chem. B 2001, 105, 4636-4646). The assemblies of PBI 1 possess very broad absorption bands compared to those of THIATS, even at low temperature (5 times broader). We interpret this observation as an indication for a very large level of disorder in the case of PBI 1 assemblies. Possible sources of disorder in aggregates of PBI 1 are discussed. Despite large quantitative differences, both aggregates show qualitatively the same temperature dependence of the Stokes shift calculated in units of fluorescence bandwidth. The observed temperature dependences are discussed in terms of exciton thermal population of different states of disordered aggregates. Unexpectedly low thermal activation energy of exciton migration is observed for PBI 1 aggregates. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
113
pages
15836 - 15842
publisher
The American Chemical Society
external identifiers
  • wos:000272037800016
  • pmid:19754082
  • scopus:72149087438
ISSN
1520-5207
DOI
10.1021/jp905246r
language
English
LU publication?
yes
id
5e4cfb0b-89d0-4f0b-86fe-2dbfdf034fc9 (old id 1483503)
date added to LUP
2009-10-08 12:50:44
date last changed
2017-09-24 03:54:42
@article{5e4cfb0b-89d0-4f0b-86fe-2dbfdf034fc9,
  abstract     = {Absorption and fluorescence spectral properties of J-aggregates of core-tetrasubstituted perylene bisimide (PBI) dyes have been investigated in the temperature range from 300 to 5 K. A special feature of the present PBI J-aggregates is that, in contrast to classical J-aggregates like that of pseudoisocyanine (PIC), the chromophores are held together not only by van-der-Waals interactions but also by hydrogen bonds. The temperature dependence of the spectral band widths and the Stokes shift for PBI 1 aggregates are compared with those for 3,3'-bis-(3-sulfopropyl)-5,5'-dichloro-9-ethylthiacarbocyanine (THIATS) J-aggregates, which have been studied in detail previously (J. Phys. Chem. B 2001, 105, 4636-4646). The assemblies of PBI 1 possess very broad absorption bands compared to those of THIATS, even at low temperature (5 times broader). We interpret this observation as an indication for a very large level of disorder in the case of PBI 1 assemblies. Possible sources of disorder in aggregates of PBI 1 are discussed. Despite large quantitative differences, both aggregates show qualitatively the same temperature dependence of the Stokes shift calculated in units of fluorescence bandwidth. The observed temperature dependences are discussed in terms of exciton thermal population of different states of disordered aggregates. Unexpectedly low thermal activation energy of exciton migration is observed for PBI 1 aggregates.},
  author       = {Kaiser, Theo E and Scheblykin, Ivan and Thomsson, Daniel and Würthner, Frank},
  issn         = {1520-5207},
  language     = {eng},
  pages        = {15836--15842},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Temperature-Dependent Exciton Dynamics in J-Aggregates-When Disorder Plays a Role.},
  url          = {http://dx.doi.org/10.1021/jp905246r},
  volume       = {113},
  year         = {2009},
}