Journal of Physical Chemistry A, volume 124, issue 9, pages 1787-1797

Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes

Radunz Sebastian 1
Kraus Werner 1
Tschiche Harald Rune 3
1
 
Department 1 − Analytical Chemistry; Reference Materials, Federal Institute for Materials Research and Testing (BAM), Richard-Willstaetter-Str. 11, 12489 Berlin, Germany
3
 
Department 7 − Chemicals and Product Safety, German Federal Institute for Risk Assessment (BfR), 10589 Berlin, Germany
Publication typeJournal Article
Publication date2020-02-10
Quartile SCImago
Q2
Quartile WOS
Q2
Impact factor2.9
ISSN10895639, 15205215
Physical and Theoretical Chemistry
Abstract
We report on the temperature- and structural-dependent optical properties and photophysics of a set of boron dipyrromethene (BODIPY) dyes with different substitution patterns of their meso-aryl subunit. Single-crystal X-ray diffraction analysis of the compounds enabled a classification of the dyes into a sterically hindered and a unhindered group. The steric hindrance refers to a blocked rotational motion of the aryl subunit around the bond connecting this moiety to the meso-position of the BODIPY core. The energy barriers related to this rotation were simulated by DFT calculations. As follows from the relatively low rotational barrier calculated to about 17 kcal/mol, a free rotation is only possible for sterically unhindered compounds. Rotational barriers of more than 40 kcal/mol determined for the sterically hindered compounds suggest an effective freezing of the rotational motion in these molecules. With the aid of temperature-dependent spectroscopic measurements, we could show that the ability to rotate directly affects the optical properties of our set of BODIPY dyes. This accounts for the strong temperature dependence of the fluorescence of the sterically unhindered compounds which show a drastic decrease in fluorescence quantum yield and a significant shortening in fluorescence lifetime upon heating. The optical properties of the sterically hindered compounds, however, are barely affected by temperature. Our results suggest a nonradiative deactivation of the first excited singlet state of the sterically unhindered compounds caused by a conical intersection of the potential energy surfaces of the ground and first excited state which is accessible by rotation of the meso-subunit. This is in good agreement with previously reported deactivation mechanisms. In addition, our results suggest the presence of a second nonradiative depopulation pathway of the first excited singlet state which is particularly relevant for the sterically hindered compounds.

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Radunz S. et al. Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes // Journal of Physical Chemistry A. 2020. Vol. 124. No. 9. pp. 1787-1797.
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Radunz S., Kraus W., Bischoff F. A., Emmerling F., Tschiche H. R., Resch-Genger U. Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes // Journal of Physical Chemistry A. 2020. Vol. 124. No. 9. pp. 1787-1797.
RIS |
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TY - JOUR
DO - 10.1021/acs.jpca.9b11859
UR - https://doi.org/10.1021%2Facs.jpca.9b11859
TI - Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes
T2 - Journal of Physical Chemistry A
AU - Radunz, Sebastian
AU - Tschiche, Harald Rune
AU - Bischoff, Florian A.
AU - Emmerling, Franziska
AU - Resch-Genger, Ute
AU - Kraus, Werner
PY - 2020
DA - 2020/02/10 00:00:00
PB - American Chemical Society (ACS)
SP - 1787-1797
IS - 9
VL - 124
SN - 1089-5639
SN - 1520-5215
ER -
BibTex |
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BibTex Copy
@article{2020_Radunz
author = {Sebastian Radunz and Harald Rune Tschiche and Florian A. Bischoff and Franziska Emmerling and Ute Resch-Genger and Werner Kraus},
title = {Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes},
journal = {Journal of Physical Chemistry A},
year = {2020},
volume = {124},
publisher = {American Chemical Society (ACS)},
month = {feb},
url = {https://doi.org/10.1021%2Facs.jpca.9b11859},
number = {9},
pages = {1787--1797},
doi = {10.1021/acs.jpca.9b11859}
}
MLA
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MLA Copy
Radunz, Sebastian, et al. “Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes.” Journal of Physical Chemistry A, vol. 124, no. 9, Feb. 2020, pp. 1787-1797. https://doi.org/10.1021%2Facs.jpca.9b11859.
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