Thermal Cis-to-Trans Isomerization of Azobenzene-Containing Molecules Enhanced by Gold Nanoparticles: An Experimental and Theoretical Study
| Autor: | Andrei V. Kabashin, Liudmila Lysyakova, Evgenii Titov, Nino Lomadze, Svetlana Santer, Peter Saalfrank |
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| Přispěvatelé: | Laboratoire Lasers, Plasmas et Procédés photoniques (LP3), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2015 |
| Předmět: |
Institut für Physik und Astronomie
Nanoparticle Photochemistry Surfaces Coatings and Films Electronic Optical and Magnetic Materials Electron transfer chemistry.chemical_compound General Energy Azobenzene chemistry Colloidal gold [SPI.OPTI]Engineering Sciences [physics]/Optics / Photonic Molecule Density functional theory Physical and Theoretical Chemistry Isomerization Cis–trans isomerism |
| Zdroj: | Journal of Physical Chemistry C Journal of Physical Chemistry C, American Chemical Society, 2015, 119 (30), pp.17369-17377. ⟨10.1021/acs.jpcc.5b02473⟩ Journal of Physical Chemistry C, 2015, 119 (30), pp.17369-17377. ⟨10.1021/acs.jpcc.5b02473⟩ |
| ISSN: | 1932-7447 1932-7455 |
| Popis: | International audience; We report on the experimental and theoretical investigation of a considerable increase in the rate for thermal cis -> trans isomerization of azobenzene-containing molecules in the presence of gold nanopartides. Experimentally, by means of UV vis spectroscopy, we studied a series of azobenzene-containing surfactants and 4-nitroazobenzene. We found that in the presence of gold,nanoparticles the thermal lifetime of the cis isomer of the azobenzenecontaining molecules was decreased by up to 3 orders of magnitude in comparison to the lifetime in solution without nanoparticles. The electron transfer between azobenzene-containing molecules and a surface of gold nanopartides is a possible reason to promote the thermal cis trans switching. To investigate the effect of electron attachment to, and withdrawal from, the azobenzene-containing molecules on the isomerization rate, we performed density functional theory calculations of activation energy barriers of the reaction together with Eyring's transition state theory calculations of the rates for azobenzene derivatives with donor and acceptor groups in para position of one of the phenyl rings, as well as for one of the azobenzene-containing surfactants. We found that activation barriers are greatly lowered for azobenzene-containing molecules, both upon electron attachment and withdrawal, which leads, in turn, to a dramatic increase in the thermal isomerization rate. |
| Databáze: | OpenAIRE |
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