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Differing Isomerization Kinetics of Azobenzene-Functionalized Self-Assembled Monolayers in Ambient Air and in Vacuum

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Fachbereich Physik, Freie Universität Berlin, 14195 Berlin, Germany
Physikalisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, 69120 Heidelberg, Germany
§ Department of Organic Chemistry, Weizmann Institute of Science, 76100 Rehovot, Israel
Cite this: Langmuir 2016, 32, 42, 10795–10801
Publication Date (Web):September 28, 2016
Copyright © 2016 American Chemical Society

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    Azobenzenealkanethiols in self-assembled monolayers (SAMs) on Au(111) exhibit reversible transcis photoisomerization when diluted with alkanethiol spacers. Using these mixed SAMs, we show switching of the linear optical and second-harmonic response. The effective switching of these surface optical properties relies on a reasonably large cross section and a high photoisomerization yield as well as a long lifetime of the metastable cis isomer. We quantified the switching process by X-ray absorption spectroscopy. The cross sections for the transcis and cistrans photoisomerization with 365 and 455 nm light, respectively, are 1 order of magnitude smaller than in solution. In vacuum, the 365 nm photostationary state comprises 50–74% of the molecules in the cis form, limited by their rapid thermal isomerization back to the trans state. In contrast, the 455 nm photostationary state contains nearly 100% trans-azobenzene. We determined time constants for the thermal cistrans isomerization of only a few minutes in vacuum and in a dry nitrogen atmosphere but of more than 1 day in ambient air. Our results suggest that adventitious water adsorbed on the surface of the SAM stabilizes the polar cis configuration of azobenzene under ambient conditions. The back reaction rate constants differing by 2 orders of magnitude underline the huge influence of the environment and, accordingly, its importance when comparing various experiments.

    We maintained a pressure of less than 3 × 10–6 mbar for 50 min.

    The polarization angle β is the angle between the electric field vector of the linearly polarized X-ray light and the plane of incidence.

    See the Supporting Information of ref 23.

    In Figure 5b, the asymptote observed in the “dark” segment is different from the asymptotes in the following “blue” segments, which might indicate deviations from first-order kinetics.

    A mixed SAM of Az12 diluted with C12 as the spacer, in which Az12 is identical to Az11 but has a dodecamethylene linker chain.

    Note that, in ref 16, the thermal isomerization rate constant is on the same order of magnitude as the effective transcis photoisomerization rate constant observed under UV light exposure; therefore, the cross section σtUV would be significantly smaller than the effective cross section given in that paper.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.6b01690.

    • Gold crystal preparation, additional NEXAFS and XPS spectra, derivation of isomerization kinetics, and isomerization kinetics of Az11 in methanol (PDF)

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