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Title: Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule

Abstract

In this study, a hybrid magnetic multilayer material of micrometric size, with highly crystalline hexagonal crystals consisting of CoAl–LDH ferromagnetic layers intercalated with thermoresponsive 4-(4 anilinophenylazo)benzenesulfonate (AO5) molecules diluted (ratio 9 : 1) with a flexible sodium dodecylsulphate (SDS) surfactant has been obtained. The resulting material exhibits thermochromism attributable to the isomerization between the azo (prevalent at room temperature) and the hydrazone (favoured at higher temperatures) tautomers, leading to a thermomechanical response. In fact, these crystals exhibited thermally induced motion triggering remarkable changes in the crystal morphology and volume. In situ variable temperature XRD of these thin hybrids shows that the reversible change into the two tautomers is reflected in a shift of the position of the diffraction peaks at high temperatures towards lower interlayer spacing for the hydrazone form, as well as a broadening of the peaks reflecting lower crystallinity and ordering due to non-uniform spacing between the layers. These structural variations between room temperature (basal spacing (BS) = 25.91 Å) and 100 °C (BS = 25.05 Å) are also reflected in the magnetic properties of the layered double hydroxide (LDH) due to the variation of the magnetic coupling between the layers. Finally and in conclusion, our study constitutesmore » one of the few examples showing fully reversible thermo-responsive breathing in a 2D hybrid material. In addition, the magnetic response of the hybrid can be modulated due to the thermotropism of the organic component that, by influencing the distance and in-plane correlation of the inorganic LDH, modulates the magnetism of the CoAl–LDH sheets in a certain range.« less

Authors:
 [1];  [2];  [2];  [3];  [4];  [4];  [5];  [1];  [2];  [1]
  1. Univ. of Valencia (Spain). Inst. de Ciencia Molecular
  2. Univ. Politecnica de Valencia (Spain). Inst. de Tecnologia Quimica (UPV-CSIC)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Univ. Complutense Madrid (Spain). Dept. Fisica Aplicada III. Inst. Pluridisciplinar
  4. Univ. Autonoma de Madrid (Spain). Centro de Investigacion de Fisica de la Materia Condensada; Univ. Autonoma de Madrid (Spain). Dept. de Fisica de la Materia Condensada
  5. Univ. Autonoma de Madrid (Spain). Centro de Investigacion de Fisica de la Materia Condensada; Univ. Autonoma de Madrid (Spain). Dept. de Quimica Inorganica
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); European Commission (EC); Ministry of Economy and Competitiveness (Spain); Consolider-Ingenio 2010-Multicat (Spain); Severo Ochoa Program (Spain); Generalitat Valenciana (Spain)
Contributing Org.:
Univ. of Valencia (Spain); Univ. Politecnica de Valencia (Spain); Univ. Autonoma de Madrid (Spain)
OSTI Identifier:
1265610
Grant/Contract Number:  
AC05-00OR22725; ERC-2009-AdG-20090325; STEMOX#239739; MAT2011-22785; MAT2012-38567-C02-01; MAT2013-46753-C2; CTQ-2011-26507; CSD2009-00050; SEV-2012-0267; FP7/2013-IEF-627386
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Abellán, Gonzalo, Jordá, Jose Luis, Atienzar, Pedro, Varela, María, Jaafar, Miriam, Gómez-Herrero, Julio, Zamora, Félix, Ribera, Antonio, García, Hermenegildo, and Coronado, Eugenio. Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule. United States: N. p., 2014. Web. doi:10.1039/c4sc03460k.
Abellán, Gonzalo, Jordá, Jose Luis, Atienzar, Pedro, Varela, María, Jaafar, Miriam, Gómez-Herrero, Julio, Zamora, Félix, Ribera, Antonio, García, Hermenegildo, & Coronado, Eugenio. Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule. United States. doi:10.1039/c4sc03460k.
Abellán, Gonzalo, Jordá, Jose Luis, Atienzar, Pedro, Varela, María, Jaafar, Miriam, Gómez-Herrero, Julio, Zamora, Félix, Ribera, Antonio, García, Hermenegildo, and Coronado, Eugenio. Thu . "Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule". United States. doi:10.1039/c4sc03460k. https://www.osti.gov/servlets/purl/1265610.
@article{osti_1265610,
title = {Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule},
author = {Abellán, Gonzalo and Jordá, Jose Luis and Atienzar, Pedro and Varela, María and Jaafar, Miriam and Gómez-Herrero, Julio and Zamora, Félix and Ribera, Antonio and García, Hermenegildo and Coronado, Eugenio},
abstractNote = {In this study, a hybrid magnetic multilayer material of micrometric size, with highly crystalline hexagonal crystals consisting of CoAl–LDH ferromagnetic layers intercalated with thermoresponsive 4-(4 anilinophenylazo)benzenesulfonate (AO5) molecules diluted (ratio 9 : 1) with a flexible sodium dodecylsulphate (SDS) surfactant has been obtained. The resulting material exhibits thermochromism attributable to the isomerization between the azo (prevalent at room temperature) and the hydrazone (favoured at higher temperatures) tautomers, leading to a thermomechanical response. In fact, these crystals exhibited thermally induced motion triggering remarkable changes in the crystal morphology and volume. In situ variable temperature XRD of these thin hybrids shows that the reversible change into the two tautomers is reflected in a shift of the position of the diffraction peaks at high temperatures towards lower interlayer spacing for the hydrazone form, as well as a broadening of the peaks reflecting lower crystallinity and ordering due to non-uniform spacing between the layers. These structural variations between room temperature (basal spacing (BS) = 25.91 Å) and 100 °C (BS = 25.05 Å) are also reflected in the magnetic properties of the layered double hydroxide (LDH) due to the variation of the magnetic coupling between the layers. Finally and in conclusion, our study constitutes one of the few examples showing fully reversible thermo-responsive breathing in a 2D hybrid material. In addition, the magnetic response of the hybrid can be modulated due to the thermotropism of the organic component that, by influencing the distance and in-plane correlation of the inorganic LDH, modulates the magnetism of the CoAl–LDH sheets in a certain range.},
doi = {10.1039/c4sc03460k},
journal = {Chemical Science},
number = 3,
volume = 6,
place = {United States},
year = {Thu Dec 04 00:00:00 EST 2014},
month = {Thu Dec 04 00:00:00 EST 2014}
}

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