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

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c4sc03460k· OSTI ID:1265610
 [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
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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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); European Commission (EC); Ministry of Economy and Competitiveness (Spain); Consolider-Ingenio 2010-Multicat (Spain); Severo Ochoa Program (Spain); Generalitat Valenciana (Spain)
Contributing Organization:
Univ. of Valencia (Spain); Univ. Politecnica de Valencia (Spain); Univ. Autonoma de Madrid (Spain)
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
OSTI ID:
1265610
Journal Information:
Chemical Science, Vol. 6, Issue 3; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 34 works
Citation information provided by
Web of Science

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Cited By (8)

Tailoring Hybrid Layered Double Hydroxides for the Development of Innovative Applications journal November 2017
Thermochromic Behavior of Azobenzene‐based Coordination Polymer with Reversible Breathing Process journal March 2019
Layered gadolinium hydroxides for low-temperature magnetic cooling journal January 2015
Preparation of two dimensional layered double hydroxide nanosheets and their applications journal January 2017
Mechanochemical methods for the preparation of intercalation compounds, from intercalation to the formation of layered double hydroxides journal January 2018
Influence of morphology in the magnetic properties of layered double hydroxides journal January 2018
Liquid phase exfoliation of carbonate-intercalated layered double hydroxides journal January 2019
High-Power Ultrasonic Synthesis and Magnetic-Field-Assisted Arrangement of Nanosized Crystallites of Cobalt-Containing Layered Double Hydroxides journal July 2019

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY