Abstract
Azobenzenealkanethiols in self-assembled monolayers (SAMs) on Au(111) exhibit reversible trans-cis 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 trans-cis and cis-trans 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 cis-trans 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.
| Original language | English |
|---|---|
| Pages (from-to) | 10795-10801 |
| Number of pages | 7 |
| Journal | Langmuir |
| Volume | 32 |
| Issue number | 42 |
| DOIs | |
| Publication status | Published - Oct 25 2016 |
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ASJC Scopus subject areas
- Materials Science(all)
- Condensed Matter Physics
- Surfaces and Interfaces
- Spectroscopy
- Electrochemistry
Cite this
Differing Isomerization Kinetics of Azobenzene-Functionalized Self-Assembled Monolayers in Ambient Air and in Vacuum. / Moldt, Thomas; Przyrembel, Daniel; Schulze, Michael; Bronsch, Wibke; Boie, Larissa; Brete, Daniel; Gahl, Cornelius; Klajn, Rafal; Tegeder, Petra; Weinelt, Martin.
In: Langmuir, Vol. 32, No. 42, 25.10.2016, p. 10795-10801.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Differing Isomerization Kinetics of Azobenzene-Functionalized Self-Assembled Monolayers in Ambient Air and in Vacuum
AU - Moldt, Thomas
AU - Przyrembel, Daniel
AU - Schulze, Michael
AU - Bronsch, Wibke
AU - Boie, Larissa
AU - Brete, Daniel
AU - Gahl, Cornelius
AU - Klajn, Rafal
AU - Tegeder, Petra
AU - Weinelt, Martin
PY - 2016/10/25
Y1 - 2016/10/25
N2 - Azobenzenealkanethiols in self-assembled monolayers (SAMs) on Au(111) exhibit reversible trans-cis 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 trans-cis and cis-trans 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 cis-trans 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.
AB - Azobenzenealkanethiols in self-assembled monolayers (SAMs) on Au(111) exhibit reversible trans-cis 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 trans-cis and cis-trans 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 cis-trans 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.
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U2 - 10.1021/acs.langmuir.6b01690
DO - 10.1021/acs.langmuir.6b01690
M3 - Article
AN - SCOPUS:84993940478
VL - 32
SP - 10795
EP - 10801
JO - Langmuir
JF - Langmuir
SN - 0743-7463
IS - 42
ER -