Resumé
| Originalsprog | Engelsk |
|---|---|
| Tidsskrift | Physical Chemistry Chemical Physics |
| Vol/bind | 2014 |
| Udgave nummer | 16 |
| Sider (fra-til) | 9128-9137 |
| ISSN | 1463-9076 |
| DOI | |
| Status | Udgivet - 2014 |
Emneord
- hyphenated
- laser
- NMR
- IR
- thioxoketones
Citer dette
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Arresting Consecutive Steps of a Photochromic Reaction: Studies of β-Thioxoketones Combining Laser Photolysis with NMR Detection. / Pietrzak, Mariusz; Dobkowski, Jacek; Gorski, Alexandr; Gawinkowski, Sylwester; Luboradzki, Roman; Kijak , Michał; Hansen, Poul Erik; Waluk, Jacek.
I: Physical Chemistry Chemical Physics, Bind 2014, Nr. 16, 2014, s. 9128-9137.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review
TY - JOUR
T1 - Arresting Consecutive Steps of a Photochromic Reaction: Studies of β-Thioxoketones Combining Laser Photolysis with NMR Detection
AU - Pietrzak, Mariusz
AU - Dobkowski, Jacek
AU - Gorski, Alexandr
AU - Gawinkowski, Sylwester
AU - Luboradzki, Roman
AU - Kijak , Michał
AU - Hansen, Poul Erik
AU - Waluk, Jacek
PY - 2014
Y1 - 2014
N2 - Photochromism of monothiodibenzoylmethane has been studied in a number of environments at different temperatures. Direct laser irradiation of a sample located in the NMR magnet allowed in situ monitoring of the phototransformation products, determining their structure, and measuring the kinetics of the back reaction. These observations, along with the data obtained using electronic and vibrational spectroscopies for rare gas matrix-isolated samples, glasses, polymers, and solutions, as well as the results of quantum-chemical calculations, provide insight into the stepwise mechanism of the photochromism in β-thioxoketones. At low temperature in rigid matrices the electronic excitation leads to the formation of the –SH exorotamer of the (Z)-enethiol tautomer. In solutions, further steps are possible, producing a mixture of two other non-chelated enethiol forms. Photoconversion efficiency strongly depends on the excitation wavelength. Analysis of the mechanisms of the photochromic processes indicates a state-specific precursor: chelated thione–enol form in the excited S2(ππ*) electronic state. The results show the potential of using laser photolysis coupled with NMR detection for the identification of phototransformation products
AB - Photochromism of monothiodibenzoylmethane has been studied in a number of environments at different temperatures. Direct laser irradiation of a sample located in the NMR magnet allowed in situ monitoring of the phototransformation products, determining their structure, and measuring the kinetics of the back reaction. These observations, along with the data obtained using electronic and vibrational spectroscopies for rare gas matrix-isolated samples, glasses, polymers, and solutions, as well as the results of quantum-chemical calculations, provide insight into the stepwise mechanism of the photochromism in β-thioxoketones. At low temperature in rigid matrices the electronic excitation leads to the formation of the –SH exorotamer of the (Z)-enethiol tautomer. In solutions, further steps are possible, producing a mixture of two other non-chelated enethiol forms. Photoconversion efficiency strongly depends on the excitation wavelength. Analysis of the mechanisms of the photochromic processes indicates a state-specific precursor: chelated thione–enol form in the excited S2(ππ*) electronic state. The results show the potential of using laser photolysis coupled with NMR detection for the identification of phototransformation products
KW - hyphenated
KW - laser
KW - NMR
KW - IR
KW - thioxoketones
KW - hyphenated
KW - laser
KW - NMR
KW - IR
KW - thioxoketones
U2 - 10.1039/C4CP00530A
DO - 10.1039/C4CP00530A
M3 - Journal article
VL - 2014
SP - 9128
EP - 9137
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 16
ER -