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Rotamer-Specific Photoisomerization of Difluorostilbenes from Transient Absorption and Transient Raman Spectroscopy.

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Title: Rotamer-Specific Photoisomerization of Difluorostilbenes from Transient Absorption and Transient Raman Spectroscopy.
Authors: Quick, M.1 quickmaq@chemie.hu-berlin.de, Dobryakov, A. L.1, Ioffe, I. N.2, Berndt, F.1, Mahrwald, R.1, Ernsting, N. P.1, Kovalenko, S. A.1
Source: Journal of Physical Chemistry B. 1/25/2018, Vol. 122 Issue 3, p1049-1059. 11p.
Subjects: Stilbene, Photoisomerization, Raman spectroscopy, Conformational isomers, Raman spectra
Abstract: Photoisomerization of 2,2'-, 3,3'-, and 4,4'-difluorostilbene (F2, F3, F4, respectively) in n-hexane, perfluoro-n-hexane, and acetonitrile is studied with broadband transient absorption (TA) and femtosecond stimulated Raman (FSR) spectroscopy and by DFT/TDDFT calculations. F2 and F3 possess three rotamers (rotational isomers) each, while F4 has one single conformation only. These differences are reflected in TA and FSR spectra. Thus F4 reveals a monoexponential decay of TA with τ1 = 172 ps in n-hexane, as expected for a single species. For F2 and F3, the decays are biexponential in all solvents, corresponding to two distinctly discerned rotamers or rotamer fractions. Specifically, for F2 in n-hexane, τ1 = 357 ps (83%) and τ2 = 62 ps (17%), and for F3 in the same solvent, τ1 = 222 ps (57%), and τ2 = 81 ps (43%). The weights in brackets agree with theoretically estimated ground-state abundances of the rotamers. Furthermore, a global fit of the TA and FSR data allows us to extract the spectra of the pure rotamers. The Raman spectra of S0 and S1 are in qualitative agreement with calculations. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Chemistry B is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Rotamer-Specific Photoisomerization of Difluorostilbenes from Transient Absorption and Transient Raman Spectroscopy.
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  Data: <searchLink fieldCode="AR" term="%22Quick%2C+M%2E%22">Quick, M.</searchLink><relatesTo>1</relatesTo><i> quickmaq@chemie.hu-berlin.de</i><br /><searchLink fieldCode="AR" term="%22Dobryakov%2C+A%2E+L%2E%22">Dobryakov, A. L.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Ioffe%2C+I%2E+N%2E%22">Ioffe, I. N.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Berndt%2C+F%2E%22">Berndt, F.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Mahrwald%2C+R%2E%22">Mahrwald, R.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Ernsting%2C+N%2E+P%2E%22">Ernsting, N. P.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Kovalenko%2C+S%2E+A%2E%22">Kovalenko, S. A.</searchLink><relatesTo>1</relatesTo>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+B%22">Journal of Physical Chemistry B</searchLink>. 1/25/2018, Vol. 122 Issue 3, p1049-1059. 11p.
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  Data: <searchLink fieldCode="DE" term="%22Stilbene%22">Stilbene</searchLink><br /><searchLink fieldCode="DE" term="%22Photoisomerization%22">Photoisomerization</searchLink><br /><searchLink fieldCode="DE" term="%22Raman+spectroscopy%22">Raman spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Conformational+isomers%22">Conformational isomers</searchLink><br /><searchLink fieldCode="DE" term="%22Raman+spectra%22">Raman spectra</searchLink>
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  Data: Photoisomerization of 2,2'-, 3,3'-, and 4,4'-difluorostilbene (F2, F3, F4, respectively) in n-hexane, perfluoro-n-hexane, and acetonitrile is studied with broadband transient absorption (TA) and femtosecond stimulated Raman (FSR) spectroscopy and by DFT/TDDFT calculations. F2 and F3 possess three rotamers (rotational isomers) each, while F4 has one single conformation only. These differences are reflected in TA and FSR spectra. Thus F4 reveals a monoexponential decay of TA with τ1 = 172 ps in n-hexane, as expected for a single species. For F2 and F3, the decays are biexponential in all solvents, corresponding to two distinctly discerned rotamers or rotamer fractions. Specifically, for F2 in n-hexane, τ1 = 357 ps (83%) and τ2 = 62 ps (17%), and for F3 in the same solvent, τ1 = 222 ps (57%), and τ2 = 81 ps (43%). The weights in brackets agree with theoretically estimated ground-state abundances of the rotamers. Furthermore, a global fit of the TA and FSR data allows us to extract the spectra of the pure rotamers. The Raman spectra of S0 and S1 are in qualitative agreement with calculations. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Physical Chemistry B is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/acs.jpcb.7b09283
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        Text: English
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      – SubjectFull: Stilbene
        Type: general
      – SubjectFull: Photoisomerization
        Type: general
      – SubjectFull: Raman spectroscopy
        Type: general
      – SubjectFull: Conformational isomers
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      – SubjectFull: Raman spectra
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      – TitleFull: Rotamer-Specific Photoisomerization of Difluorostilbenes from Transient Absorption and Transient Raman Spectroscopy.
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              Text: 1/25/2018
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