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

[Image: see text] 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...

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Autores principales: Markey, Karen, Krüger, Martin, Seidler, Tomasz, Reinsch, Helge, Verbiest, Thierry, De Vos, Dirk E., Champagne, Benoît, Stock, Norbert, van der Veen, Monique A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2017
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5694968/
https://www.ncbi.nlm.nih.gov/pubmed/29170688
http://dx.doi.org/10.1021/acs.jpcc.7b09190
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author Markey, Karen
Krüger, Martin
Seidler, Tomasz
Reinsch, Helge
Verbiest, Thierry
De Vos, Dirk E.
Champagne, Benoît
Stock, Norbert
van der Veen, Monique A.
author_facet Markey, Karen
Krüger, Martin
Seidler, Tomasz
Reinsch, Helge
Verbiest, Thierry
De Vos, Dirk E.
Champagne, Benoît
Stock, Norbert
van der Veen, Monique A.
author_sort Markey, Karen
collection PubMed
description [Image: see text] 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 Al(3+), Ga(3+), or In(3+) 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.
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spelling pubmed-56949682017-11-21 Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks Markey, Karen Krüger, Martin Seidler, Tomasz Reinsch, Helge Verbiest, Thierry De Vos, Dirk E. Champagne, Benoît Stock, Norbert van der Veen, Monique A. J Phys Chem C Nanomater Interfaces [Image: see text] 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 Al(3+), Ga(3+), or In(3+) 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. American Chemical Society 2017-10-17 2017-11-16 /pmc/articles/PMC5694968/ /pubmed/29170688 http://dx.doi.org/10.1021/acs.jpcc.7b09190 Text en Copyright © 2017 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Markey, Karen
Krüger, Martin
Seidler, Tomasz
Reinsch, Helge
Verbiest, Thierry
De Vos, Dirk E.
Champagne, Benoît
Stock, Norbert
van der Veen, Monique A.
Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
title Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
title_full Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
title_fullStr Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
title_full_unstemmed Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
title_short Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
title_sort emergence of nonlinear optical activity by incorporation of a linker carrying the p-nitroaniline motif in mil-53 frameworks
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5694968/
https://www.ncbi.nlm.nih.gov/pubmed/29170688
http://dx.doi.org/10.1021/acs.jpcc.7b09190
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