TY - JOUR
T1 - Emergence of Nonlinear Optical Activity by Incorporation of a Linker Carrying the p-Nitroaniline Motif in MIL-53 Frameworks
AU - Markey, Karen
AU - Krüger, Martin
AU - Seidler, Tomasz
AU - Reinsch, Helge
AU - Verbiest, Thierry
AU - De Vos, Dirk E.
AU - Champagne, Benoît
AU - Stock, Norbert
AU - Van Der Veen, Monique A.
PY - 2017/11/16
Y1 - 2017/11/16
N2 - 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.
AB - 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.
UR - http://resolver.tudelft.nl/uuid:cc97773d-6ce9-4a99-8fde-1b02a56604fc
UR - http://www.scopus.com/inward/record.url?scp=85034658278&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.7b09190
DO - 10.1021/acs.jpcc.7b09190
M3 - Article
AN - SCOPUS:85034658278
SN - 1932-7447
VL - 121
SP - 25509
EP - 25519
JO - The Journal of Physical Chemistry C
JF - The Journal of Physical Chemistry C
IS - 45
ER -