The high intrinsic spin and long spin relaxation time of manganese-12-acetate (Mn(12)) makes it an archetypical single molecular magnet. While these characteristics have been measured on bulk samples, questions remain whether the magnetic properties replicate themselves in surface supported isolated molecules, a prerequisite for any application. Here we demonstrate that electrospray ion beam deposition facilitates grafting of intact Mn(12) molecules on metal as well as ultrathin insulating surfaces enabling submolecular resolution imaging by scanning tunneling microscopy. Using scanning tunneling spectroscopy we detect spin excitations from the magnetic ground state of the molecule at an ultrathin boron nitride decoupling layer. Our results are supported by density functional theory based calculations and establish that individual Mn(12) molecules retain their intrinsic spin on a well chosen solid support.
Nanoparticles of iron(II) triazole salts have been prepared from water-organic microemulsions. The mean size of the nanoparticles can be tuned down to 6 nm in diameter, with a narrow size distribution. A sharp spin transition from the low spin (LS) to the high spin (HS) state is observed above room temperature, with a 30-40-K-wide thermal hysteresis. The same preparation can yield second generation nanoparticles containing molecular alloys by mixing triazole with triazole derivatives, or from metallic mixtures of iron(II) and zinc(II). In these nanoparticles of 10-15 nm, the spin transition "moves" towards lower temperatures, reaching a 316 K limit for the cooling down transition and maintaining a thermal hysteresis over 15-20-K-wide. The nanoparticles were characterized by dynamic light scattering, TEM, and AFM, after deposition on gold or silicon surfaces. The spin transition was characterized by magnetic susceptibility measurements and EXAFS (in solid samples after solvent removal) and also by the color change between the LS (violet) and HS (colorless) states in an organic solvent suspension. The discovery of bistable magnetic nanoparticles of 6 nm with a wide thermal hysteresis above room temperature showcases the actual possibilities of spin crossover materials for nanotechnological applications.
AFM images are always affected by artifacts arising from tip convolution effects, resulting in a decrease in the lateral resolution of this technique. The magnitude of such effects is described by means of geometrical considerations, thereby providing better understanding of the convolution phenomenon. We demonstrate that for a constant tip radius, the convolution error is increased with the object height, mainly for the narrowest motifs. Certain influence of the object shape is observed between rectangular and elliptical objects with the same height. Such moderate differences are essentially expected among elongated objects; in contrast they are reduced as the object aspect ratio is increased. Finally, we propose an algorithm to study the influence of the size, shape and aspect ratio of different nanometric motifs on a flat substrate. Indeed, with this algorithm, convolution artifacts can be extended to any kind of motif including real surface roughness. From the simulation results we demonstrate that in most cases the real motif's width can be estimated from AFM images without knowing its shape in detail.
Prussian blue (PB) represents a simple, economical, and eco-friendly system as cathode material for sodium-ion batteries (SIBs). However, structural problems usually worsen its experimental performance thus motivating the search for alternative synthetic strategies and the formation of composites that compensate these deficiencies. Herein, a straightforward approach for the preparation of PB/MoS 2 -based nanocomposites is presented. MoS 2 provides a 2D active support for the homogeneous nucleation of porous PB nanocrystals, which feature superior surface areas than those obtained by other methodologies, giving rise to a compact PB shell covering the full flake. The nanocomposite exhibits an excellent performance as cathode for SIBs with discharge capacity values up to 177 mA h g −1 and a specific capacitance of 354 F g −1 . These values are even larger for the intercalation of K + ions (up to 215 mA h g −1 , reaching a specific capacitance of 489 F g −1 ). Compared to similar composites, superior performance can be ascribed to a synergistic effect of the coordination compound with the 2D material.
New approaches to the fabrication of planar devices based on materials by design are critical for the development of organic electronics. [1][2][3][4] Conventional nanolithography techniques [5] (top-down), as well as self-organization of functional elements that take up proper positions and shapes and establish connections with other components (bottom-up) have been applied. [6][7][8][9] These approaches make use of specific interactions between the components and the substrate, such as hydrophobicity/hydrophilicity, electrostatic forces, or protein recognition. Several scanning-probe-based nanolithographies, [10][11][12] printing-based methods, [13] and parallel approaches based on the transfer of nanoparticles from a stamp [5] are also being pursued. The discovery that magnetic hysteresis can also arise from high-spin molecules with a significant magnetic anisotropy has prompted interest in dodecanuclear manganese complexes of the general formula Mn 12 O 12 (RCOO) 12 (H 2 O) 12 .
Chirality-induced spin selectivity (CISS), the effect of helical molecules acting as room temperature hard magnets that confer spin polarization to electrical current, is an intriguing effect with potential applications in nanospintronics. In this scenario, molecules that are paramagnetic as well as helical would introduce a new degree of freedom in the same nano-scale device that has not been explored so far. Here, in order to investigate this idea, we propose the preparation of self-assembled monolayers (SAMs) based on a helical lanthanide binding tag peptide (LnLBTC) on a ferromagnetic substrate. We confirmed room temperature spin filtering of LnLBTC SAMs by well-established electrochemical approach and by direct local spin transport measurements in solid state devices. The latter were studied by a common liquid-metal drop electron transport system, easily implemented for spin dependent measurements. Electrochemistry shows an averaged spin polarization (SP) of ~5% in presence of a saturation magnetic field (H = 350 mT) while local measurements performed in solid state showed a SP of ~50 20% thanks to the reduction of the contribution of pure electron transport in non-covered areas. Calculations showed that conduction electrons interact strongly with the coordinated lanthanide ion, meaning a fixed chirality-based spin filtering can coexist with a spin filtering that is dependent on the polarization of the magnetic metal ion. This opens the door to all-organic single-molecule memristive devices.
Electrostatic interactions drive the adsorption of polycationic single-molecule magnets onto anionic monolayers self-assembled on gold surfaces. Well-isolated magnetic clusters have been deposited and characterized using scanning tunneling microscopy and X-ray photoemission spectroscopy.
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