Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV - Vis and IR spectroscopies

Gotard Burdzinski; Michel Sliwa; Yunlong Zhang; Stephanie Delbaere

doi:10.1021/jp2055238

Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV - Vis and IR spectroscopies

Gotard Burdzinski
, Michel Sliwa
, Yunlong Zhang
, Stephanie Delbaere

Research output: Contribution to journal › Article › peer-review

Abstract

Photochemistry of 4-methyl-5-carboethoxy-1,2,3-thiadiazole (MCT) in solution was studied at room temperature using UV - vis and IR transient absorption spectroscopies (λ _ex = 266 nm). Three deactivation pathways are discussed: thiirene formation, thioketene generation, and the internal conversion by repopulating MCT in the ground state. Ultrafast techniques show a very fast rise (<0.4ps) of thiirene species in acetonitrile, possibly as a result of a rearrangement in the singlet excited state of MCT in concert with molecular nitrogen extrusion. The remarkable stability of thiirene in solution on a millisecond time scale is limited by the process of dimerization (thiirene - thiirene, thiirene - thioketene). NMR analysis permitted identification of stable photoproducts as 1,3-dithietane, 1,3-dithiole, and thiophene derivatives. (Figure presented)

Original language	English
Pages (from-to)	14300-14305
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	115
Issue number	50
DOIs	https://doi.org/10.1021/jp2055238
Publication status	Published - 22 Dec 2011
Externally published	Yes

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@article{69122d4b241a4b22a46a585e99e4da04,

title = "Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV - Vis and IR spectroscopies",

abstract = "Photochemistry of 4-methyl-5-carboethoxy-1,2,3-thiadiazole (MCT) in solution was studied at room temperature using UV - vis and IR transient absorption spectroscopies (λ ex = 266 nm). Three deactivation pathways are discussed: thiirene formation, thioketene generation, and the internal conversion by repopulating MCT in the ground state. Ultrafast techniques show a very fast rise (<0.4ps) of thiirene species in acetonitrile, possibly as a result of a rearrangement in the singlet excited state of MCT in concert with molecular nitrogen extrusion. The remarkable stability of thiirene in solution on a millisecond time scale is limited by the process of dimerization (thiirene - thiirene, thiirene - thioketene). NMR analysis permitted identification of stable photoproducts as 1,3-dithietane, 1,3-dithiole, and thiophene derivatives. (Figure presented)",

author = "Gotard Burdzinski and Michel Sliwa and Yunlong Zhang and Stephanie Delbaere",

year = "2011",

month = dec,

day = "22",

doi = "10.1021/jp2055238",

language = "English",

volume = "115",

pages = "14300--14305",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

number = "50",

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TY - JOUR

T1 - Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV - Vis and IR spectroscopies

AU - Burdzinski, Gotard

AU - Sliwa, Michel

AU - Zhang, Yunlong

AU - Delbaere, Stephanie

PY - 2011/12/22

Y1 - 2011/12/22

N2 - Photochemistry of 4-methyl-5-carboethoxy-1,2,3-thiadiazole (MCT) in solution was studied at room temperature using UV - vis and IR transient absorption spectroscopies (λ ex = 266 nm). Three deactivation pathways are discussed: thiirene formation, thioketene generation, and the internal conversion by repopulating MCT in the ground state. Ultrafast techniques show a very fast rise (<0.4ps) of thiirene species in acetonitrile, possibly as a result of a rearrangement in the singlet excited state of MCT in concert with molecular nitrogen extrusion. The remarkable stability of thiirene in solution on a millisecond time scale is limited by the process of dimerization (thiirene - thiirene, thiirene - thioketene). NMR analysis permitted identification of stable photoproducts as 1,3-dithietane, 1,3-dithiole, and thiophene derivatives. (Figure presented)

AB - Photochemistry of 4-methyl-5-carboethoxy-1,2,3-thiadiazole (MCT) in solution was studied at room temperature using UV - vis and IR transient absorption spectroscopies (λ ex = 266 nm). Three deactivation pathways are discussed: thiirene formation, thioketene generation, and the internal conversion by repopulating MCT in the ground state. Ultrafast techniques show a very fast rise (<0.4ps) of thiirene species in acetonitrile, possibly as a result of a rearrangement in the singlet excited state of MCT in concert with molecular nitrogen extrusion. The remarkable stability of thiirene in solution on a millisecond time scale is limited by the process of dimerization (thiirene - thiirene, thiirene - thioketene). NMR analysis permitted identification of stable photoproducts as 1,3-dithietane, 1,3-dithiole, and thiophene derivatives. (Figure presented)

U2 - 10.1021/jp2055238

DO - 10.1021/jp2055238

M3 - Article

C2 - 22054095

AN - SCOPUS:84055200887

SN - 1089-5639

VL - 115

SP - 14300

EP - 14305

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 50

ER -

Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV - Vis and IR spectroscopies

Abstract

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