Plasmon-enhanced two-photon-induced isomerization for highly-localized light-based actuation of inorganic/organic interfaces

Lim, Chang-Keun, Li, Xin, Li, Yue, Drew, Kurt L. M., Palafox-Hernandez, J. Pablo, Tang, Zhenghua, Baev, Alexander, Kuzmin, Andrey N., Knecht, Marc R., Walsh, Tiffany R., Swihart, Mark T., Ågren, Hans and Prasad, Paras N. 2016, Plasmon-enhanced two-photon-induced isomerization for highly-localized light-based actuation of inorganic/organic interfaces, Nanoscale, vol. 8, no. 7, pp. 4194-4202, doi: 10.1039/c5nr07973j.

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Title Plasmon-enhanced two-photon-induced isomerization for highly-localized light-based actuation of inorganic/organic interfaces
Author(s) Lim, Chang-Keun
Li, Xin
Li, Yue
Drew, Kurt L. M.
Palafox-Hernandez, J. Pablo
Tang, Zhenghua
Baev, Alexander
Kuzmin, Andrey N.
Knecht, Marc R.
Walsh, Tiffany R.ORCID iD for Walsh, Tiffany R.
Swihart, Mark T.
Ågren, Hans
Prasad, Paras N.
Journal name Nanoscale
Volume number 8
Issue number 7
Start page 4194
End page 4202
Total pages 9
Publisher Royal Society of Chemistry
Place of publication London, Eng.
Publication date 2016-02-21
ISSN 2040-3372
Keyword(s) Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Physics, Applied
Science & Technology - Other Topics
Materials Science
Summary Two-photon initiated photo-isomerization of an azobenzene moiety adsorbed on silver nanoparticles (Ag NPs) is demonstrated. The azobenzene is linked to a materials-binding peptide that brings it into intimate contact with the Ag NP surface, producing a dramatic enhancement of its two-photon absorbance. An integrated modeling approach, combining advanced conformational sampling with Quantum Mechanics/Capacitance Molecular Mechanics and response theory, shows that charge transfer and image charges in the Ag NP generate local fields that enhance two-photon absorption of the cis isomer, but not the trans isomer, of adsorbed molecules. Moreover, dramatic local field enhancement is expected near the localized surface plasmon resonance (LSPR) wavelength, and the LSPR band of the Ag NPs overlaps the azobenzene absorbance that triggers cis to trans switching. As a result, the Ag NPs enable two-photon initiated cis to trans isomerization, but not trans to cis isomerization. Confocal anti-Stokes fluorescence imaging shows that this effect is not due to local heating, while the quadratic dependence of switching rate on laser intensity is consistent with a two-photon process. Highly localized two-photon initiated switching could allow local manipulation near the focal point of a laser within a 3D nanoparticle assembly, which cannot be achieved using linear optical processes.
Language eng
DOI 10.1039/c5nr07973j
Field of Research 030303 Optical Properties of Materials
030302 Nanochemistry and Supramolecular Chemistry
030704 Statistical Mechanics in Chemistry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
ERA Research output type C Journal article
Copyright notice ©2016, The Royal Society of Chemistry
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