Glass transition of one-dimensional molecular chains of <i>p</i>-nitroaniline confined in AlPO4-5 nanopores revealed by dielectric spectroscopy

Wübbenhorst, Michael; Klap, G.J.; Jansen, J.C.; Bekkum, H. van; Turnhout, J. van

doi:10.1063/1.479864

Cited by 17 publications

(9 citation statements)

References 20 publications

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“…in a dielectric spectroscopy study of the cooperative dynamics of PNA in AlPO-5. 20 The size of the domains that can be distinguished by SHGM varies between a few hundred nanometres, which is close to the diffraction limit (as in Fig. 3c), to 410 mm (as in Fig.…”

supporting

confidence: 64%

Mapping of the organization of p-nitroaniline in SAPO-5 by second-harmonic generation microscopy

Veen¹,

Noyen²,

Sels³

et al. 2010

Phys. Chem. Chem. Phys.

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Second-harmonic generation microscopy (SHGM) has been employed to study crystals of zeolite-like material SAPO-5 filled with p-nitroaniline (PNA). The SHG and 2-photon fluorescence response of PNA in the one-dimensional channels readily reveals the pore accessibility; intergrown crystallites containing hexagonal pyramidal components and internal diffusion barriers are found next to seemingly perfect crystals. The sensitivity of second-harmonic generation to molecular orientation allowed for mapping of the domains of differently organized PNA. Dense domains of highly aligned PNA alternate with dilute zones with loosely aligned PNA.

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supporting

confidence: 64%

Mapping of the organization of p-nitroaniline in SAPO-5 by second-harmonic generation microscopy

Veen¹,

Noyen²,

Sels³

et al. 2010

Phys. Chem. Chem. Phys.

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“…29 , 30 To obtain a polar material benefiting from the SONLO properties of PNA, researchers successfully adsorbed PNA molecules into zeolites, leading to overall polarity. 31 − 36 However, zeolites have limited chemical modification and processing possibilities. MOFs can alleviate these issues, as they offer tunability, combined with ease of processing and the possibility to obtain polarity.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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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.

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“…Many efforts have been undertaken in the last 2 decades to study the deviation of the cooperative dynamics of glass forming liquids from their bulk behavior, when they are confined to nanometer dimensions. While the existence of confinement effects has been demonstrated by numerous work on very different systems including ultra-thin films [1][2][3], nanoporous glasses and zeolites [4][5][6][7], a general conclusive picture of the nature and the origin of such deviations has not yet been achieved, since experimental effects usually dependent on the particular approach and the specific molecular system and the confining geometry. In this context, porous hosts providing spherical or cylindrical pores, with typical diameters of few nanometers probably represent a very popular system to study confinement effects on the dynamics of low molecular mass glass formers [4] mainly due to the possibility to prepare robust and large volume samples suitable for bulk-techniques like calorimetry, NMR and neutron scattering.…”

Section: Introductionmentioning

confidence: 99%

Dynamics in ultrathin liquid films studied by simultaneous dielectric spectroscopy (DRS) and organic molecular beam deposition (OMBD)

Wübbenhorst

Capponi

Napolitano

et al. 2010

Eur. Phys. J. Spec. Top.

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Real-time dielectric relaxation spectroscopy for a molecular beam deposited glass forming liquids is proposed as a versatile approach for the study of the dynamic glass transition in geometric confinement. To achieve the highest sensitivity down to monomolecular organic layers in a wide frequency range (0.1-10 7 Hz) during simultaneous deposition and desorption, we have used µm spaced interdigitated electrodes under ultrahigh vacuum conditions. Experiments using glycerol deposited on fused silica at-40 • C revealed a dielectric glass transition process for a layer thickness as low as 0.7 nm. While its peak position hardly changes upon thickness reduction, a clear broadening of the relaxation peak is observed that implies an increasing heterogeneous mobility scenario for the thinnest films caused by molecules being part of a reduced (at the substrate) or enhanced (free surface) mobility layer. This finding is supported by desorption experiments that reveal a strong retardation of the desorption rate for films below 1 nm.

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Glass transition of one-dimensional molecular chains of p-nitroaniline confined in AlPO4-5 nanopores revealed by dielectric spectroscopy

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Cited by 17 publications

References 20 publications

Mapping of the organization of p-nitroaniline in SAPO-5 by second-harmonic generation microscopy

Mapping of the organization of p-nitroaniline in SAPO-5 by second-harmonic generation microscopy

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

Dynamics in ultrathin liquid films studied by simultaneous dielectric spectroscopy (DRS) and organic molecular beam deposition (OMBD)

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