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Vibrational sum-frequency generation study of molecular structure, sterical constraints and nonlinear optical switching contrast of mixed alkyl-azobenzene self-assembled monolayers

  • Saira Riaz and Gernot Friedrichs EMAIL logo

Abstract

Self-assembled monolayers (SAMs) of azobenzene (AB) functionalized alkyl thiols on gold diluted with simple alkyl thiols provide a straightforward way to photochromic surfaces with high and tunable photoswitching efficiency. Trans-cis isomerization of the AB molecule changes the physical properties of the surface, including the nonlinear optical (NLO) response. Vibrational sum-frequency generation (VSFG) spectroscopy as a nonlinear type of laser spectroscopy offers surface- and orientation-sensitive insight into the molecular structure of mixed SAMs. In this study, VSFG as well as ultraviolet-visible (UV/Vis) spectroscopy has been employed to investigate the morphology, molecular structure, and NLO response of mixed SAMs with systematically varied surface composition. Methylazobenzene (MeAB) has been used as the molecular switch with the methyl substituent serving as orientational VSFG marker. Both short-chain and long-chain alkyl thiol co-ligands have been used to gain insight into the interplay between SAM structure and sterical constraints that are known to limit the free switching volume. Underlining the dominating role of sterical effects for controlling photochromic properties, a strong inhibition of the photoswitching efficiency and NLO response has been observed for the SAMs with an alkyl thiol co-ligand long enough to spatially extend into the layer of the MeAB chromophore. Overall, with <12% signal change, the relative NLO switching contrasts remained low in all cases. VSFG spectral trends clearly revealed that the presumably higher photoswitching efficiency upon dilution with the co-ligand is counteracted by a loss of structural order of the chromophore.


Corresponding author: Gernot Friedrichs, Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Str. 1, 24118, Kiel, Germany, E-mail:

Dedicated to Prof. Friedrich Temps on the occasion of his 65th birthday


Acknowledgment

The authors thank Dr. Kristian Laß for many valuable discussions and his deep involvement in the preliminary VSFG studies of AB functionalized Au samples in the framework of the Bachelor theses of Bent Gorgel and Uta-Corinna Stange. Thanks to the anonymous reviewers for many valuable comments and for pointing us to the very promising opportunities of resonantly enhanced SHG experiments. This work is dedicated to Prof. Dr. Friedrich Temps on the occasion of his 65th birthday and acknowledges many years of rewarding collaboration. In particular, we thank him for his continued interest in the progress of this research project.

  1. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: Deutsche Forschungsgemeinschaft, CRC/SFB 677 “Function by Switching”.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material https://doi.org/10.1515/jtse-2019-0044.

Received: 2020-02-28
Accepted: 2020-05-04
Published Online: 2020-07-27
Published in Print: 2020-08-27

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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