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Molecules 2017, 22(11), 1844; doi:10.3390/molecules22111844

Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study

1
Laboratory of Chemistry and Bioengineering, Tampere University of Technology, P.O. Box 541, FI-33101 Tampere, Finland
2
Department of Applied Physics, Aalto University, P.O. Box 15100, FI-00076 Espoo, Finland
3
Laboratory of Supramolecular and Bio-Nanomaterials (SupraBioNanoLab), Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, I-20131 Milano, Italy
Present address: Institute of Organic Chemistry, University of Duisburg-Essen, Universitätstraße 7, 45117 Essen, Germany.
*
Author to whom correspondence should be addressed.
Received: 10 October 2017 / Revised: 25 October 2017 / Accepted: 26 October 2017 / Published: 28 October 2017
(This article belongs to the Special Issue Photoresponsive Polymers)
View Full-Text   |   Download PDF [1790 KB, uploaded 28 October 2017]   |  

Abstract

In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer–azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer–azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer–azobenzene complexes. View Full-Text
Keywords: surface-relief grating; azobenzene; halogen bonding; supramolecular; photoresponsive surface-relief grating; azobenzene; halogen bonding; supramolecular; photoresponsive
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Stumpel, J.E.; Saccone, M.; Dichiarante, V.; Lehtonen, O.; Virkki, M.; Metrangolo, P.; Priimagi, A. Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study. Molecules 2017, 22, 1844.

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