Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone

Alexander Gorski, Yevgen Posokhov, Bjarke Knud Vilster Hansen, Jens Spanget-Larsen, Jan Jasny, Fritz Duus, Poul Erik Hansen, Jacek Waluk

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

Photochromism of p-methylthiobenzoylacetone (1) has been studied in argon and xenon cryogenic matrices. Application of linearly polarized light to induce the phototransformation resulted in partial alignment of both the initial structure and the photochromic product. Different orientations were achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining the structures of the most stable ground state species and of the photoproduct. Similarly to the recently reported cases of thioacetylacetone and monothiodibenzoylmethane, the initial structure of 1 corresponds to an intramolecularly hydrogen-bonded enol form, and the photochromic species to an “open”, nonchelated enethiolic form. Vibrational assignments have been made for both species, greatly helped by the analysis of the LD spectra. It is concluded that DFT calculations for 1 quite reliably predict not only vibrational frequencies and intensities, but also transition moment directions, in both IR and electronic spectra.
OriginalsprogEngelsk
TidsskriftChemical Physics
Vol/bind328
Udgave nummer1-3
Sider (fra-til)205-215
Antal sider11
ISSN0301-0104
DOI
StatusUdgivet - 2006

Citer dette

Gorski, Alexander ; Posokhov, Yevgen ; Hansen, Bjarke Knud Vilster ; Spanget-Larsen, Jens ; Jasny, Jan ; Duus, Fritz ; Hansen, Poul Erik ; Waluk, Jacek. / Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone. I: Chemical Physics. 2006 ; Bind 328, Nr. 1-3. s. 205-215.
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title = "Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone",
abstract = "Photochromism of p-methylthiobenzoylacetone (1) has been studied in argon and xenon cryogenic matrices. Application of linearly polarized light to induce the phototransformation resulted in partial alignment of both the initial structure and the photochromic product. Different orientations were achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining the structures of the most stable ground state species and of the photoproduct. Similarly to the recently reported cases of thioacetylacetone and monothiodibenzoylmethane, the initial structure of 1 corresponds to an intramolecularly hydrogen-bonded enol form, and the photochromic species to an “open”, nonchelated enethiolic form. Vibrational assignments have been made for both species, greatly helped by the analysis of the LD spectra. It is concluded that DFT calculations for 1 quite reliably predict not only vibrational frequencies and intensities, but also transition moment directions, in both IR and electronic spectra.",
keywords = "Photochromism, Thioxoketones, Linear Dichroism, Polarization Spectroscopy, Matrix Isolation",
author = "Alexander Gorski and Yevgen Posokhov and Hansen, {Bjarke Knud Vilster} and Jens Spanget-Larsen and Jan Jasny and Fritz Duus and Hansen, {Poul Erik} and Jacek Waluk",
year = "2006",
doi = "10.1016/j.chemphys.2006.06.033",
language = "English",
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pages = "205--215",
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Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone. / Gorski, Alexander; Posokhov, Yevgen; Hansen, Bjarke Knud Vilster; Spanget-Larsen, Jens; Jasny, Jan; Duus, Fritz; Hansen, Poul Erik; Waluk, Jacek.

I: Chemical Physics, Bind 328, Nr. 1-3, 2006, s. 205-215.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Photochromism and polarization spectroscopy of p-methylthiobenzoylacetone

AU - Gorski, Alexander

AU - Posokhov, Yevgen

AU - Hansen, Bjarke Knud Vilster

AU - Spanget-Larsen, Jens

AU - Jasny, Jan

AU - Duus, Fritz

AU - Hansen, Poul Erik

AU - Waluk, Jacek

PY - 2006

Y1 - 2006

N2 - Photochromism of p-methylthiobenzoylacetone (1) has been studied in argon and xenon cryogenic matrices. Application of linearly polarized light to induce the phototransformation resulted in partial alignment of both the initial structure and the photochromic product. Different orientations were achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining the structures of the most stable ground state species and of the photoproduct. Similarly to the recently reported cases of thioacetylacetone and monothiodibenzoylmethane, the initial structure of 1 corresponds to an intramolecularly hydrogen-bonded enol form, and the photochromic species to an “open”, nonchelated enethiolic form. Vibrational assignments have been made for both species, greatly helped by the analysis of the LD spectra. It is concluded that DFT calculations for 1 quite reliably predict not only vibrational frequencies and intensities, but also transition moment directions, in both IR and electronic spectra.

AB - Photochromism of p-methylthiobenzoylacetone (1) has been studied in argon and xenon cryogenic matrices. Application of linearly polarized light to induce the phototransformation resulted in partial alignment of both the initial structure and the photochromic product. Different orientations were achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining the structures of the most stable ground state species and of the photoproduct. Similarly to the recently reported cases of thioacetylacetone and monothiodibenzoylmethane, the initial structure of 1 corresponds to an intramolecularly hydrogen-bonded enol form, and the photochromic species to an “open”, nonchelated enethiolic form. Vibrational assignments have been made for both species, greatly helped by the analysis of the LD spectra. It is concluded that DFT calculations for 1 quite reliably predict not only vibrational frequencies and intensities, but also transition moment directions, in both IR and electronic spectra.

KW - Photochromism

KW - Thioxoketones

KW - Linear Dichroism

KW - Polarization Spectroscopy

KW - Matrix Isolation

U2 - 10.1016/j.chemphys.2006.06.033

DO - 10.1016/j.chemphys.2006.06.033

M3 - Journal article

VL - 328

SP - 205

EP - 215

JO - Chemical Physics

JF - Chemical Physics

SN - 0301-0104

IS - 1-3

ER -