Carbon Nanotubes: In-Situ Growth of Ultrathin Films of NiFe-LDHs: Towards a Hierarchical Synthesis of Bamboo-Like Carbon Nanotubes (Adv. Mater. Interfaces 6/2014)

ChemInform Abstract: Coherence and Organisation in Lanthanoid Complexes: From Single Ion Magnets to Spin Qubits

Molecular magnetism is reaching a degree of development that will allow for the rational design of sophisticated systems. Among these, here we will focus on those that display single-molecule magnetic behaviour, i.e. classical memories, and on magnetic molecules that can be used as molecular spin qubits, the irreducible components of any quantum technology. Compared with candidates developed from physics, a major advantage of molecular spin qubits stems from the power of chemistry for the tailored and inexpensive synthesis of new systems for their experimental study; in particular, the so-called lanthanoid-based single-ion magnets, which have for a long time been one of the hottest topics i…

Tailoring magnetic properties of electrodeposited thin films of the molecule-based magnet Cr5.5(CN)12 11.5H2O

This paper reports on molecular-based magnetic thin films of Prussian blue analogues (PBA) with high critical temperatures composed of mixed-valence chromium cyanides. The thin films of PBA were synthesized by means of electrodeposition technique. Morphology and magnetic study are presented in a function of electrochemical deposition conditions. We present the electrochemical methods as a promising and effective tool for preparing molecular-based magnetic thin films of Prussian blue analogue.

In-Situ Growth of Ultrathin Films of NiFe-LDHs: Towards a Hierarchical Synthesis of Bamboo-Like Carbon Nanotubes

The synthesis of ultrathin films (UTFs) of NiFe-LDHs has been achieved by means of an in situ hydrothermal approach, leading to a flat disposition of the LDH crystallites on the substrate, in clear contrast to the most common perpendicular orientation reported to date. Experimental factors like time of synthesis or the nature of the substrate, seem to play a crucial role during the growing process. The 2D morphology of the NiFe-LDH crystallites was kept after a calcination procedure, leading to a topotactic transformation into mixed-metal oxide platelets. Hereby, in order to study the catalytic behavior of our samples, a chemical vapor deposition process is explored upon the as-synthesized …

Exchange coupling in an electrodeposited magnetic bilayer of Prussian blue analogues

Bilayers of Prussian blue analogues (PBA) constituted of hard and soft magnets have been fabricated by means of electrochemical deposition. This method affords a good contact between two PBA thin films of nanometer thickness. Complete characterization of the resulting system has been performed, which has allowed the determination of the preservation of the chemical identity of both materials during the electrodeposition and the establishment of a clear interface between them. The magnetic behavior of the bilayer can be explained in terms of an exchange-spring magnet.

Energy Storage: Giant Enhancement in the Supercapacitance of NiFe–Graphene Nanocomposites Induced by a Magnetic Field (Adv. Mater. 28/2019)

CVD synthesis of carbon spheres using NiFe-LDHs as catalytic precursors: structural, electrochemical and magnetoresistive properties

The gram-scale synthesis of carbon spheres with a diameter of ca. 740 nm has been achieved by means of a chemical vapour deposition method using NiFe-layered double hydroxides as a solid catalytic precursor. The presence of the catalyst (FeNi3) allows controlling the final size distribution, resulting in a monodisperse sample. Their structural properties exhibited a high degree of graphitization according to their ID/IG ratio. In addition, their morphological features were unveiled by FIB-SEM and HRTEM, showing that they are formed by solid inner cores, and presenting labile chain-like structures due to accretion procedures. The solution and posterior sonication of the samples in toluene ga…

Near Isotropic D4d Spin Qubits as Nodes of a Gd(III)-Based Metal-Organic Framework

Embedding coherent spin motifs in reproducible molecular building blocks is a promising pathway for the realization of quantum technologies. Three-dimensional (3D) MOFs are a versatile platform for the rational design of extended structures employing coordination chemistry. Here, we report the synthesis and characterization of a gadolinium(III)-based MOF, [Gd(bipyNO)4](TfO)3·xMeOH (bipyNO = bipyridine,N,N′-dioxide; TfO = triflate; and MeOH = methanol) (quMOF-1), which presents a unique coordination geometry that leads to a tiny magnetic anisotropy (in terms of D, an equivalent zero-field splitting would be achieved by D = 0.006 cm–1) even compared with regular Gd(III) complexes. Pulsed elec…

Magneto-Optical Properties of Electrodeposited Thin Films of the Molecule-Based Magnet Cr5.5(CN)12·11.5H2O

Prof. E. Coronado , M. Makarewicz , J. P. Prieto-Ruiz , Dr. H. Prima-Garcia , Dr. F. M. Romero Instituto de Ciencia Molecular (ICMol) Universitat de Valencia C/Catedratico Jose Beltran, 2, 46980-Paterna, Spain E-mail: eugenio.coronado@uv.es; helena.prima@uv.es; fmrm@uv.es

Magnetic and magneto-optical properties of nickel hexacyanoferrate/chromate thin films

One of the most important challenges of modern science and technology is the quest for novel and tuneable materials, the properties of which can be widely controlled by chemical modifications or external stimuli. Simultaneously, an interest in the development of magnetic thin films also gains significant attention. In the current paper we bring together both these challenges and present a study of a new type of low-dimensional nickel hexacyanoferrate/chromate system. Thin films were obtained by the "layer by layer" deposition technique, where the ratio of Fe/Cr was controlled by the dipping sequence. The scope of this work is a comprehensive analysis of structural, spectroscopic and magneti…

Influence of the covalent grafting of organic radicals to graphene on its magnetoresistance

Graphene was obtained by direct exfoliation of graphite in o-dichlorobenzene (oDCB) or benzylamine, and further functionalized with 4,4′-[(1,3-dioxo-1,3-propanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl-1-piperidinyloxy] (1-TEMPO) organic radicals by using the Bingel–Hirsch cyclopropanation reaction. Here, the use of different solvents permits variation of the density of radicals anchored to the carbon layers. Covalent grafting is unambiguously demonstrated by TGA, μ-Raman, XPS and EPR measurements, which also rule out spurious physisorption. Our transport measurements indicate that the conduction mechanism varies as a function of the density of radicals grafted to the carbon layers. Moreover, t…

Spin-Polarized Hopping Transport in Magnetically Tunable Rare-Earth Quinolines

Dr. A. Bedoya-Pinto, Prof. F. Casanova, Prof. L. E. Hueso CIC nanoGUNE Consolider olosa T Hiribidea 76 , 20018 Donostia–San Sebastian , Spain E-mail: a.bedoya@nanogune.eu; l.hueso@nanogune.eu Dr. H. Prima-Garcia, Prof. E. Coronado Instituto de Ciencia Molecular (ICMoL) Universidad de Valencia C/Catedratico Jose Beltran 2 , E-46980 Valencia , Spain Prof. F. Casanova, Prof. L. E. Hueso IKERBASQUE, Basque Foundation for Science E-48011 Bilbao , Spain

Coherence and organisation in lanthanoid complexes: from single ion magnets to spin qubits

Molecular magnetism is reaching a degree of development that will allow for the rational design of sophisticated systems. Among these, here we will focus on those that display single-molecule magnetic behaviour, i.e. classical memories, and on magnetic molecules that can be used as molecular spin qubits, the irreducible components of any quantum technology. Compared with candidates developed from physics, a major advantage of molecular spin qubits stems from the power of chemistry for the tailored and inexpensive synthesis of new systems for their experimental study; in particular, the so-called lanthanoid-based single-ion magnets, which have for a long time been one of the hottest topics i…

Design of Molecular Spintronics Devices Containing Molybdenum Oxide as Hole Injection Layer

Giant Enhancement in the Supercapacitance of NiFe–Graphene Nanocomposites Induced by a Magnetic Field

The rapid rise in energy demand in the past years has prompted a search for low-cost alternatives for energy storage, supercapacitors being one of the most important devices. It is shown that a dramatic enhancement (≈1100%, from 155 to 1850 F g-1 ) of the specific capacitance of a hybrid stimuli-responsive FeNi3 -graphene electrode material can be achieved when the charge/discharge cycling is performed in the presence of an applied magnetic field of 4000 G. This result is related to an unprecedented magnetic-field-induced metal segregation of the FeNi3 nanoparticles during the cycling, which results in the appearance of small Ni clusters (<5 nm) and, consequently, in an increase in pseudoca…

Graphene enhances the magnetoresistance of FeNi3nanoparticles in hierarchical FeNi3–graphene nanocomposites

An increase in the giant magnetoresistance of FeNi3 nanoparticles of 20 times has been observed in FeNi3–graphene nanocomposites synthesized using NiFe-layered double hydroxide hybrids as precursors. The magnetic, transport and magneto-transport properties of these nanocomposites are studied and compared with those of the pure FeNi3 nanoparticles. The hierarchical structure and hybrid composition of these magnetic nanocomposites lead to the observation of two unusual magneto-transport properties, namely (i) an enhancement in the low-field magnetoresistance effects, and (ii) a crossover from negative to positive MR upon cooling down the sample.

Enhancing Light Emission in Interface Engineered Spin-OLEDs through Spin-Polarized Injection at High Voltages

The quest for a spin-polarized organic light-emitting diode (spin-OLED) is a common goal in the emerging fields of molecular electronics and spintronics. In this device, two ferromagnetic (FM) electrodes are used to enhance the electroluminescence intensity of the OLED through a magnetic control of the spin polarization of the injected carriers. The major difficulty is that the driving voltage of an OLED device exceeds a few volts, while spin injection in organic materials is only efficient at low voltages. The fabrication of a spin-OLED that uses a conjugated polymer as bipolar spin collector layer and ferromagnetic electrodes is reported here. Through a careful engineering of the organic/…

Zinc oxide nanocrystals as electron injecting building blocks for plastic light sources

Hybrid inorganic–organic light emitting devices (HyLEDs) employing ZnO nanocrystals as one of their metal oxide contacts lead to very bright devices on plastic substrates with performances superior to those obtained from the rigid counterparts employing planar films of bulk ZnO. The superior performance is related to the increase in the bandgap of the ZnO nanocrystals caused by quantum confinement effects. We demonstrate that this effect diminishes with increasing annealing temperature of the ZnO nanocrystal layer due to a gradual decrease of the bandgap towards the bulk ZnO value. Therefore, best performances were obtained with room temperature processing of the ZnO nanocrystals.

Sublimable chloroquinolinate lanthanoid single-ion magnets deposited on ferromagnetic electrodes

A new family of chloroquinolinate lanthanoid complexes of the formula A+[Ln(5,7Cl2q)4]−, with Ln = Y3+, Tb3+ and Dy3+ and A+ = Na+, NEt4+ and K0.5(NEt4)0.5+, is studied, both in bulk and as thin films. Several members of the family are found to present single-molecule magnetic behavior in bulk. Interestingly, the sodium salts can be sublimed under high vacuum conditions retaining their molecular structures and magnetic properties. These thermally stable compounds have been deposited on different substrates (Al2O3, Au and NiFe). The magnetic properties of these molecular films show the appearance of cusps in the zero-field cooled curves when they are deposited on permalloy (NiFe). This indic…

Gd-based single-ion magnets with tunable magnetic anisotropy: Molecular design of spin qubits

et al.

Magnetic ordering in an (Fe0.2Cr0.8)1.5[Cr(CN)6] Prussian blue analogue studied with synchrotron radiation based spectroscopies

The appearance of magnetic order in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O Prussian blue analogue at low temperature has been investigated by means of synchrotron radiation-based X-ray absorption spectroscopy and X-ray magnetic circular dichroism. With the help of ligand field multiplet analysis we have been able to identify the oxidation states of the metallic cations present in the sample and their evolution with temperature. Our experiments reveal that the appearance of ferromagnetic order is triggered by the transformation of CrIII cations to CrII high-spin caused by a transfer of electrons from the Fe to the Cr resulting in an increase of the magnetic interactions within the (Cr, Cr) subla…

Self-assembled monolayers on a ferromagnetic permalloy surface.

Self-assembled monolayers (SAMs) are nowadays broadly used as surface protectors or modifiers and play a key role in many technological applications. This has motivated the study of their formation in all kind of materials; however, and despite the current interest in molecular spintronics, the study of SAMs on ferromagnetic surfaces remains almost unexplored. In this paper, we report for the first time a methodology for the formation of SAMs of n-alkylphosphonic acids on permalloy in ambient conditions. The formed monolayers have been fully characterized by means of contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, matrix assisted laser desorption ioniz…

MOKE magnetometry as a probe of surface magnetic impurities in electropolymerized magnetic thin films of the Prussian blue analogue Fe3[Cr(CN)6]2·15 H2O

A magneto-optical Kerr effect (MOKE) study has been performed on electrodeposited thin films of the Prussian blue analogue Fe3[Cr(CN)6]2·15H2O (1). This study reveals the onset of hysteretic magnetic signals at temperatures above 60 K, in contrast with magnetic susceptibility measurements which indicate a Curie temperature of 23 K for this ferromagnetic film. The origin of this discrepancy is due to the presence of amorphous iron oxide particles that accumulate in the surface of the material. This report illustrates the potential of MOKE magnetometry for the detection of surface chemical impurities that remain elusive using bulk magnetic techniques.

Binding Sites, Vibrations and Spin-Lattice Relaxation Times in Europium(II)-Based Metallofullerene Spin Qubits.

Abstract To design molecular spin qubits with enhanced quantum coherence, a control of the coupling between the local vibrations and the spin states is crucial, which could be realized in principle by engineering molecular structures via coordination chemistry. To this end, understanding the underlying structural factors that govern the spin relaxation is a central topic. Here, we report the investigation of the spin dynamics in a series of chemically designed europium(II)‐based endohedral metallofullerenes (EMFs). By introducing a unique structural difference, i. e. metal‐cage binding site, while keeping other molecular parameters constant between different complexes, these manifest the ke…

Evaluation of Superparamagnetic Silica Nanoparticles for Extraction of Triazines in Magnetic in-Tube Solid Phase Microextraction Coupled to Capillary Liquid Chromatography

The use of magnetic nanomaterials for analytical applications has increased in the recent years. In particular, magnetic nanomaterials have shown great potential as adsorbent phase in several extraction procedures due to the significant advantages over the conventional methods. In the present work, the influence of magnetic forces over the extraction efficiency of triazines using superparamagnetic silica nanoparticles (NPs) in magnetic in tube solid phase microextraction (Magnetic-IT-SPME) coupled to CapLC has been evaluated. Atrazine, terbutylazine and simazine has been selected as target analytes. The superparamagnetic silica nanomaterial (SiO2-Fe3O4) deposited onto the surface of a capil…

Spin polarization in electrodeposited thin films of the molecule-based magnetic semiconductor Cr5.5(CN)12·11.5H2O

The magnetoresistance (MR) effect of thin films of the Prussian Blue Analogue (PBA) Cr5.5(CN)12·11.5H2O, prepared by electrochemical deposition, has been measured using the standard two-point probe method. This molecule-based ferrimagnetic material, with a Tc = 240 K, exhibits MR up to 2% at 6 T and 200 K.

Photoinduced effects on the magnetic properties of the (Fe0.2Cr0.8)1.5[Cr(CN)6] Prussian blue analogue

International audience; One of the most attractive characteristics of some Prussian blue derivatives is the sensitivity of their magnetic properties to the irradiation with light. In this work photoinduced effects in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O PBA have been studied by means of X-ray-based spectroscopies and magnetometry. It is found that the photosensitivity of this compound is mostly centred on the Fe cations: the exposure to green light induces a transfer of electrons from them to the Cr that provokes a reversal of the previously existing linkage isomerization and increases the elastic strain caused by the misfit of the unit cells of the Fe–NC–Cr and Cr–NC–Cr sublattices. The gree…

Intravenous SPION-labeled adipocyte-derived stem cells targeted to the brain by magnetic attraction in a rat stroke model: An ultrastructural insight into cell fate within the brain

Abstract Mesenchymal stem cell therapy after stroke is a promising option investigated in animal models and clinical trials. The intravenous route is commonly used in clinical settings guaranteeing an adequate safety profile although low yields of engraftment. In this report, rats subjected to ischemic stroke were injected with adipose-derived stem cells (ADSCs) labeled with superparamagnetic iron oxide nanoparticles (SPIONs) applying an external magnetic field in the skull to retain the cells. Although most published studies demonstrate viability of ADSCs, only a few have used ultrastructural techniques. In our study, the application of a local magnetic force resulted in a tendency for hig…

Magnetic In-Tube Solid Phase Microextraction

We report a new in-tube solid phase microextraction approach named magnetic in-tube solid phase microextraction, magnetic-IT-SPME. Magnetic-IT-SPME has been developed, taking advantage of magnetic microfluidic principles with the aim to improve extraction efficiency of IT-SPME systems. First, a magnetic hybrid material formed by Fe(3)O(4) nanoparticles supported on SiO(2) was synthesized and immobilized in the surface of a bared fused silica capillary column to obtain a magnetic adsorbent extraction phase. The capillary column was placed inside a magnetic coil that allowed the application of a variable magnetic field. Acetylsalicylic acid, acetaminophen, atenolol, diclofenac, and ibuprofen …

Graphene electrochemical responses sense surroundings

Abstract Graphite oxide (GO) paper, obtained by direct filtration of exfoliated GO in water over PTFE membrane filters, was reduced by using hydrazine vapours. The graphene-paper thus obtained was characterized by the combination of different techniques. The electrochemical characterization by cyclic voltammetry, chronoamperometry and chronopotentiometry presents a strong influence of the working conditions: temperature, electrolyte concentration and current on the electrochemical responses, indicating a good ability of the material to sense ambient and working conditions. Electrochemical devices based on graphene are expected to work as dual, and simultaneous, sensing-actuators.

Cover Picture. Energy Storage: Giant Enhancement in the Supercapacitance of NiFe-Graphene Nanocomposites Induced by a Magnetic Field (Adv. Mater. 28/2019)

The application of external magnetic fields to NiFe–graphene nanocomposites during the galvanostatic charge/discharge cycles induces a dramatic metal phase segregation, forming nanometric metal clusters of Ni with an outstanding electrochemical activity. This metal segregation leads to an enhancement in the capacitance of the nanocomposite, as described by Gonzalo Abellán, Eugenio Coronado, and co-workers in article number 1900189. PNICTOCHEM 804110 (G.A.) CIDEGENT/2018/001