Emergence of nonlinear optical activity by incorporation of a linker carrying the p-nitroaniline motif in MIL-53 frameworks

Karen Markey, Martin Krüger, Tomasz Seidler, Helge Reinsch, Thierry Verbiest, Dirk De Vos, Benoît Champagne, Norbert Stock, Monique A. Van Der Veen

Research output: Contribution to journalArticlepeer-review


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.
Original languageEnglish
Pages (from-to)25509-25519
Number of pages11
JournalJournal of Physical Chemistry C
Issue number45
Publication statusPublished - 16 Nov 2017


  • nonlinear optical activity
  • frameworks
  • quantum chemistry


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  • Subvention - Professeur de recherche Francqui

    Nakano, M. & Castet, F.


    Project: Research

  • PAI n°P7/05 - FS2: Functional Supramolecular Systems (FS2)

    CHAMPAGNE, B., De Vos, D., Van der Auweraer, M., Jérôme, C., Lazzaroni, R., Marin, G., Jonas, A., Du Prez, F., Vanderzande, D., Van Tendeloo, G., Van Speybroeck, V., NENON, S. & STAELENS, N.


    Project: Research

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