Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks

Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks

Markey, Karen (Katholieke Universiteit Leuven)
Krüger, Martin (Christian-Albrechts-Universität zu Kiel)
Seidler, Tomasz (Jagiellonian University; University of Namur)
Reinsch, Helge (Christian-Albrechts-Universität zu Kiel)
Verbiest, Thierry (Katholieke Universiteit Leuven)
De Vos, Dirk E. (Katholieke Universiteit Leuven)
Champagne, Benoît (University of Namur)
Stock, Norbert (Christian-Albrechts-Universität zu Kiel)
van der Veen, M.A. (TU Delft ChemE/Catalysis Engineering)

2017-11-16

p-Nitroaniline presents the typical motif of a second-order nonlinear optically (NLO) active molecule. However, because of its crystallization in an antiparallel and hence centrosymmetric structure, the NLO activity is lost. In this contribution, the p-nitroaniline motif was built successfully into the MIL-53 metal-organic framework. More precisely, MIL-53 was synthesized with 2-amino-5-nitroterephthalate as organic linker, with Al³⁺, Ga³⁺, or In³⁺ as inorganic cation. The Al and Ga structures are polar, as confirmed by second-harmonic generation microscopy, yielding stable NLO materials. Indeed, they contain a 22-36% surplus of the dipolar 2-amino-5-nitro-terephthalate oriented in a parallel fashion. The indium compound was shown to be less crystalline and centrosymmetric. Ab initio modeling of the second-order NLO response shows that the Al and Ga materials show a response comparable to typical inorganic commercial NLO materials such as KDP. As a hybrid material, capable of low-temperature synthesis and processing and the ultrafast NLO responses associated with organic materials, this material can potentially provide an interesting venue for applications with respect to traditional inorganic NLO materials.

http://resolver.tudelft.nl/uuid:cc97773d-6ce9-4a99-8fde-1b02a56604fc

https://doi.org/10.1021/acs.jpcc.7b09190

1932-7447

The Journal of Physical Chemistry C, 121 (45), 25509-25519

Institutional Repository

journal article

© 2017 Karen Markey, Martin Krüger, Tomasz Seidler, Helge Reinsch, Thierry Verbiest, Dirk E. De Vos, Benoît Champagne, Norbert Stock, M.A. van der Veen