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  On the electronic and geometrical structure of the trans- and cis-isomer of tetra-tert-butyl-azobenzene on Au(111)

Schmidt, R., Hagen, S., Brete, D., Carley, R., Gahl, C., Dokic, J., et al. (2010). On the electronic and geometrical structure of the trans- and cis-isomer of tetra-tert-butyl-azobenzene on Au(111). Interfacial Systems Chemistry: Out of the Vacuum, Through the Liquid, Into the Cell. doi:10.1039/b924409c.

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Item Permalink: https://hdl.handle.net/11858/00-001M-0000-0010-F5FF-6 Version Permalink: https://hdl.handle.net/11858/00-001M-0000-0010-F5FF-6
Genre: Journal Article

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 Creators:
Schmidt, Roland, Author
Hagen, Sebastian1, Author           
Brete, Daniel, Author
Carley, Robert, Author
Gahl, Cornelius, Author
Dokic, Jadranka, Author
Saalfrank, Peter, Author
Hecht, Stefan, Author
Tegeder, Petra, Author
Weinelt, Martin, Author
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1Physical Chemistry, Fritz Haber Institute, Max Planck Society, ou_634546              

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 Abstract: Near edge X-ray absorption fine structure and X-ray photoelectron spectroscopy have been employed to follow the reversible trans to cis isomerization of tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). For one monolayer the molecules adopt an adsorption geometry characteristic of the trans-TBA isomer. The azo-bridge (N = N) is aligned nearly parallel to the surface and the phenyl rings exhibit a planar orientation with a small tilt angle ≤ 4° with respect to the surface normal. Illumination of the molecular layer at 455 nm triggers the trans to cis isomerization which is associated with a pronounced change of the geometrical and electronic structure. The N1s to π* transition of the central azo-bridge shifts by 0.45 ± 0.05 eV to higher photon energy and the transition dipole moment (TDM) is tilted by 59 ± 5° with respect to the surface normal. The π -system of one phenyl ring is tilted by about 30° with respect to the surface normal, while the second ring plane is oriented nearly perpendicular to the surface. This reorientation is supported by a shift and broadening of the C–H resonances associated with the tert-butyl legs of the molecule. These findings support a configuration of the photo-switched TBA molecule on Au(111) which is comparable to the cis-isomer of the free molecule. In the photo-stationary state 53 ± 5% of the TBA molecules are switched to the cis configuration. Thermal activation induces the back reaction to trans-TBA.

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Language(s): eng - English
 Dates: 2010-03-23
 Publication Status: Issued
 Pages: -
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 Rev. Type: Peer
 Identifiers: eDoc: 476544
URI: http://www.rsc.org/publishing/journals/CP/article.asp?doi=b924409c
URI: http://www.rsc.org/ej/CP/2010/b924409c.pdf
DOI: 10.1039/b924409c
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Title: Interfacial Systems Chemistry: Out of the Vacuum, Through the Liquid, Into the Cell
Source Genre: Issue
 Creator(s):
Gölzhäuser, Armin, Editor
Wöll, Christoph, Editor
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Title: Physical Chemistry Chemical Physics
  Alternative Title : Phys. Chem. Chem. Phys. PCCP
Source Genre: Journal
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Pages: - Volume / Issue: 12 (17) Sequence Number: - Start / End Page: 4488 - 4497 Identifier: -