Hybrid interfaces in layered hydroxides: magnetic and multifunctional superstructures by design

Rabu, Pierre; Delahaye, Émilie; Rogez, Guillaume

doi:10.1515/ntrev-2015-0017

Cited by 16 publications

(22 citation statements)

References 174 publications

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“…Indeed, the observed changes in the magnetism cannot be explained by changes in the Co II ( T d ) ratio, according to previous reports for α‐Co II hydroxychloride [21] and α‐Co II hydroxyhalides [20] . Additionally, the observed anomalous switching in the magnetic coupling, which is strongly dependent on the number of carbon atoms, cannot solely be explained based on d BS enhancement or dipolar interactions [5, 6, 25] . The changes in the magnetic nature of the layers must be related with the different orientation and/or the torsion of the organic molecules that modify the coupling among both sublattices ( O h and T d ), where the covalent functionalization with bridging molecules must play a unique role.…”

Section: Methodsmentioning

confidence: 61%

“…The hybrid approach has been widely used for the development and design of novel materials with tuneable chemical and physical properties at the nanoscale [1–4] . In this context, layered two‐dimensional (2D) systems, especially those based on earth‐abundant metals, are playing a key role, as they are often forming hybrid materials, which are convenient for a plethora of applications ranging from biomedicine, catalysis or magnetism, to energy storage and conversion [5–12] . Among others, layered hydroxides stand out due to their unparalleled chemical versatility which allows a precise control of their composition at the atomic or molecular level [13] …”

Section: Methodsmentioning

confidence: 99%

“…Generally, the synthesis of hybrid layered hydroxides requires hydrothermal conditions at elevated temperatures (100–250 °C) and a post recrystallization process for anion exchange [5, 6] . However, these time‐consuming procedures do not guarantee obtaining of pure crystallographic phases [28] .…”

Section: Methodsmentioning

confidence: 99%

“…[1][2][3][4] In this context, layered two-dimensional (2D) systems, especially those based on earth-abundant metals, are playing ak ey role, as they are often forming hybridm aterials, which are convenient for ap le-thora of applications rangingf rom biomedicine, catalysis or magnetism, to energy storage and conversion. [5][6][7][8][9][10][11][12] Among others, layered hydroxides stand out due to their unparalleled chemicalversatility which allows aprecise control of their compositionatt he atomic or molecular level. [13] Layered double hydroxides( LDHs) take as pecial role in the layered hydroxidef amily as they exhibit purely electrostatic interactions between the layers and the intercalated anions.…”

mentioning

confidence: 99%

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The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd–Even Effect of the Organic Spacer

Oestreicher

Hunt

Dölle

et al. 2020

Chemistry A European J

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A dramatic change in the magnetic behaviour, which solely depends on the parity of the organic linker molecules, has been found in a family of layered CoII hydroxides covalently functionalized with dicarboxylic molecules. These layered hybrid materials have been synthesized at room temperature using a one‐pot procedure through the epoxide route. While hybrids connected by odd alkyl chains exhibit coercive fields (Hc) below ca. 3500 Oe and show spontaneous magnetization at temperatures (TM) below 20 K, hybrids functionalized with even alkyl chains behave as hard magnets with Hc>5500 Oe and display a TM higher than 55 K. This intriguing behaviour was studied by density functional theory with the incorporation of a Hubbard term (DFT+U) calculations, unveiling the structural subtleties underlying this observation. Indeed, the different molecular orientation exhibited by the even/odd alkyl chains, and the orientation of the covalently linked carboxylic groups modify the intensity of the magnetic coupling of both octahedral and tetrahedral in‐plane sublattices, thus strongly affecting the magnetic properties of the hybrid. These findings offer an outstanding level of tuning in the molecular design of hybrid magnetic materials based on layered hydroxides.

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Section: Methodsmentioning

confidence: 61%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd–Even Effect of the Organic Spacer

Oestreicher

Hunt

Dölle

et al. 2020

Chemistry A European J

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“…Copper hydroxide acetate Cu 2 (OH) 3 CH 3 COO·H 2 O (CuOHAc) is the precursor of a whole class of hybrid organic–inorganic materials that are made of inorganic sheets separated by alkyl chains (such as alkyl sulfates and carboxylates) or conjugated molecules (such as fluorene phosphonates) [ 1 – 3 ]. The interest in Cu 2 (OH) 3 X systems stems from their tunable magnetic properties, strongly dependent on the nature of the organic ligands.…”

Section: Introductionmentioning

confidence: 99%

The role of 2D/3D spin-polarization interactions in hybrid copper hydroxide acetate: new insights from first-principles molecular dynamics

Chaker¹,

Ori²,

Boero³

et al. 2017

Beilstein J. Nanotechnol.

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The magnetic properties response of the layered hybrid material copper hydroxide acetate Cu 2 (OH) 3 CH 3 COO·H 2 O is studied as a function of the applied pressure within first-principles molecular dynamics. We are able to elucidate the interplay between the structural properties of this material and its magnetic character, both at the local (atomic) level and at the bulk level. We performed a detailed analysis of the intralayer spin configurations occurring for each value of the imposed projection along the z-axis for the total spin and of the applied pressure. The transition from an antiferromagnetic to a ferromagnetic state at high pressure (above 3 GPa) goes along with a vanishing difference between the spin polarizations pertaining to each layer. Therefore, at high pressure, copper hydroxide acetate is a ferromagnet with no changes of spin polarization in the direction perpendicular to the inorganic layers.857

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The Role of Covalent Functionalization in the Thermal Stability and Decomposition of Hybrid Layered Hydroxides

Oestreicher

Abellán

Coronado

2020

Physica Rapid Research Ltrs

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Hybrid organic-inorganic materials represent one of the hottest research topics in materials science. The close structureproperty relationship exhibited in these materials gives rise to a wide variety of applications in fields ranging from biomedicine, catalysis or magnetism to energy storage and conversion. [1-4] Layered and 2D systems, especially those based on earthabundant metals, are playing a key role in the hybrid materials family. The possibility of combining their physical, chemical, and mechanical properties, and the precise control over their structures, placed them in a privileged position. [5-12] Among others, layered hydroxides (LHs) offer a broad range of possibilities due to their tunable chemistry, which allows to modify at will both the inorganic layers and (in)organic intercalated anions. [13] Layered double hydroxides (LDHs) constitute the most famous member of the LHs family exhibiting purely electrostatic sheet/anion interactions. These lamellar systems display hydrotalcite-like structures composed of positive charged sheets where both M II and M III octahedral cations can be tuned. [14] In line with that, hybrid LDHs have been proposed, among others, used for stimuli-responsive materials, or as a precursor for the synthesis of carbon-based nanocomposites of interest in energy storage and conversion. [15-17] In all cases, the main properties are governed by the chemical nature of both components (inorganic host and organic guest) and the interaction between them, which is always electrostatic. In the search of new levels of functionality and complexity, different functionalization strategies have been explored, mainly based in the covalent functionalization (e.g., sylilation) of the interface, resulting in improved absorption properties but slight modifications of the magnetic or electrochemical properties. [18] Along this front, α-Co II hydroxides (or simonkolleite-like structures) are positioned as key members in the LHs family, because they can be considered as naturally occurring covalently functionalized LHs. They present two coordination environments, octahedral centers-Co II (O h)-within the layers, as in the case of LDHs and tetrahedral ones-Co II (T d)-attached to both sides by 3OH bridges. The fourth position can be used to graft different inorganic to organic ligands (Scheme 1). [19] The electronic and magnetic properties can be tuned by changing ligand and/or Co II (T d) ratio, resulting in more conductive systems (mainly by ligand to metal charge transfer) with higher magnetization temperatures (T M) as to the related LDHs. [20-22] Moreover, as recently reported by our group, in hybrid α-Co II hydroxydicarboxylates, Co 5 (OH) 8 [(CH 2) n (COO) 2 ] with n ranging from 1 to 8, the magnetic behavior can be dramatically modified by changing the parity of the organic linker: whereas odd members present T M < 20 K the even ones have T M > 55 K. [23] These results demonstrate that the nature of the interaction between the inorganic layers and the organic guest is crucial for determinin...

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Hybrid interfaces in layered hydroxides: magnetic and multifunctional superstructures by design

Cited by 16 publications

References 174 publications

The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd–Even Effect of the Organic Spacer

The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd–Even Effect of the Organic Spacer

The role of 2D/3D spin-polarization interactions in hybrid copper hydroxide acetate: new insights from first-principles molecular dynamics

The Role of Covalent Functionalization in the Thermal Stability and Decomposition of Hybrid Layered Hydroxides

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