Arresting Consecutive Steps of a Photochromic Reaction: Studies of β-Thioxoketones Combining Laser Photolysis with NMR Detection

Mariusz Pietrzak, Jacek Dobkowski, Alexandr Gorski, Sylwester Gawinkowski, Roman Luboradzki, Michał Kijak , Poul Erik Hansen, Jacek Waluk

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

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
OriginalsprogEngelsk
TidsskriftPhysical Chemistry Chemical Physics
Vol/bind2014
Udgave nummer16
Sider (fra-til)9128-9137
ISSN1463-9076
DOI
StatusUdgivet - 2014

Emneord

  • hyphenated
  • laser
  • NMR
  • IR
  • thioxoketones

Citer dette

Pietrzak, Mariusz ; Dobkowski, Jacek ; Gorski, Alexandr ; Gawinkowski, Sylwester ; Luboradzki, Roman ; Kijak , Michał ; Hansen, Poul Erik ; Waluk, Jacek. / Arresting Consecutive Steps of a Photochromic Reaction: Studies of β-Thioxoketones Combining Laser Photolysis with NMR Detection. I: Physical Chemistry Chemical Physics. 2014 ; Bind 2014, Nr. 16. s. 9128-9137.
@article{b3b73370b59c4a83a323154e3b54789f,
title = "Arresting Consecutive Steps of a Photochromic Reaction: Studies of β-Thioxoketones Combining Laser Photolysis with NMR Detection",
abstract = "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",
keywords = "hyphenated, laser, NMR, IR, thioxoketones, hyphenated, laser, NMR, IR, thioxoketones",
author = "Mariusz Pietrzak and Jacek Dobkowski and Alexandr Gorski and Sylwester Gawinkowski and Roman Luboradzki and Michał Kijak and Hansen, {Poul Erik} and Jacek Waluk",
year = "2014",
doi = "10.1039/C4CP00530A",
language = "English",
volume = "2014",
pages = "9128--9137",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "16",

}

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 tidsskriftTidsskriftartikelForskningpeer 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 -