Engineering On‐Surface Spin Crossover: Spin‐State Switching in a Self‐Assembled Film of Vacuum‐Sublimable Functional Molecule

The realization of spin‐crossover (SCO)‐based applications requires study of the spin‐state switching characteristics of SCO complex molecules within nanostructured environments, especially on surfaces. Except for a very few cases, the SCO of a surface‐bound thin molecular film is either quenched or heavily altered due to: (i) molecule–surface interactions and (ii) differing intermolecular interactions in films relative to the bulk. By fabricating SCO complexes on a weakly interacting surface, the interfacial quenching problem is tackled. However, engineering intermolecular interactions in thin SCO active films is rather difficult. Here, a molecular self‐assembly strategy is proposed to fabricate thin spin‐switchable surface‐bound films with programmable intermolecular interactions. Molecular engineering of the parent complex system [Fe(H₂B(pz)₂)₂(bpy)] (pz = pyrazole, bpy = 2,2′‐bipyridine) with a dodecyl (C₁₂) alkyl chain yields a classical amphiphile‐like functional and vacuum‐sublimable charge‐neutral Fe^II complex, [Fe(H₂B(pz)₂)₂(C₁₂‐bpy)] (C₁₂‐bpy = dodecyl[2,2′‐bipyridine]‐5‐carboxylate). Both the bulk powder and 10 nm thin films sublimed onto either quartz glass or SiO_x surfaces of the complex show comparable spin‐state switching characteristics mediated by similar lamellar bilayer like self‐assembly/molecular interactions. This unprecedented observation augurs well for the development of SCO‐based applications, especially in molecular spintronics.     

Multifunctional Nanoparticle@MOF Core–Shell Nanostructures

Controllable integration of inorganic nanoparticles (NPs) and metal–organic frameworks (MOFs) is leading to the creation of many new multifunctional materials. In this Research News, an emerging type of core–shell nanostructure, in which the inorganic NP cores are encapsulated by the MOF shells, is briefly introduced. Unique functions originating from the property synergies of different types of inorganic NP cores and MOF shells are highlighted, and insight into their future development is suggested. It is highly expected that this Research News could arouse research enthusiasm on such NP@MOF core–shell nanostructures, which have great application potential in devices, energy, the environment, and medicine.     

Core–Shell Assembled Nanoparticles as Catalysts

The deliberate tailoring of nanoparticles supported on oxides, dispersed in dendrimers and encapsulated in monolayer shells could lead to novel catalytic applications. The study of core–shell assembled gold or alloy nanoparticles for electrocatalytic oxidation of carbon monoxide and methanol stems, in part, from recent insights in core–shell reactivities and, in part, from surprising findings of catalytic activities of oxide‐supported gold nanoparticles. Monolayer‐encapsulated metallic nanoparticles serve as intriguing model building blocks towards catalysts. Whether such core–shell nanoparticles can in general be developed into aggregation‐ and poison‐resistant catalysts of high catalytic activities rests with our capabilities in catalytic activation and structural manipulation.     

Observation of Self‐Assembled Core–Shell Structures in Epitaxially Embedded TbErAs Nanoparticles

Self‐assembled core–shell structured rare‐earth nanoparticles (TbErAs) are observed in a III–V semiconductor host matrix (In_0.53Ga_0.47As) nominally lattice‐matched to InP, grown via molecular beam epitaxy. Atom probe tomography demonstrates that the TbErAs nanoparticles have a core–shell structure, as seen both in the tomographic atom‐by‐atom reconstruction and concentration profiles. A simple thermodynamic model is created to determine when it is energetically favorable to have core–shell structures; the results strongly agree with the observations.     

Electrical Detection of Spin Precession in Freely Suspended Graphene Spin Valves on Cross‐Linked Poly(methyl methacrylate)

Spin injection and detection is achieved in freely suspended graphene using cobalt electrodes and a nonlocal spin‐valve geometry. The devices are fabricated with a single electron‐beam‐resist poly(methyl methacrylate) process that minimizes both the fabrication steps and the number of (aggressive) chemicals used, greatly reducing contamination and increasing the yield of high‐quality, mechanically stable devices. As‐grown devices can present mobilities exceeding 10⁴ cm² V^?1 s^?1 at room temperature and, because the contacts deposited on graphene are only exposed to acetone and isopropanol, the method is compatible with almost any contacting material. Spin accumulation and spin precession are studied in these nonlocal spin valves. Fitting of Hanle spin precession data in bilayer and multilayer graphene yields a spin relaxation time of ～125‐250 ps and a spin diffusion length of 1.7‐1.9 μm at room temperature.     

Magnetic Nanoplatelet‐Based Spin Memory Device Operating at Ambient Temperatures

There is an increasing demand for realizing a simple Si based universal memory device working at ambient temperatures. In principle, nonvolatile magnetic memory can operate at low power consumption and high frequencies. However, in order to compete with existing memory technology, size reduction and simplification of the used material systems are essential. In this work, the chiral‐induced spin selectivity effect is used along with 30–50 nm ferromagnetic nanoplatelets in order to realize a simple magnetic memory device. The vertical memory is Si compatible, easy to fabricate, and in principle can be scaled down to a single nanoparticle size. Results show clear dual magnetization behavior with threefold enhancement between the one and zero states. The magnetization of the device is accompanied with large avalanche like noise that is ascribed to the redistribution of current densities due to spin accumulation inducing coupling effects between the different nanoplatelets.     

Dotted Core–Shell Nanoparticles for T1‐Weighted MRI of Tumors

Gd‐based T ₁‐weighted contrast agents have dominated the magnetic resonance imaging (MRI) contrast agent market for decades. Nevertheless, they are reported to be nephrotoxic and the U.S. Food and Drug Administration has issued a general warning concerning their use. In order to reduce the risk of nephrotoxicity, the MRI performance of the Gd‐based T ₁‐weighted contrast agents needs to be improved to allow a much lower dosage. In this study, novel dotted core–shell nanoparticles (FeGd‐HN3‐RGD2) with superhigh r ₁ value (70.0 mM^?1 s^?1) and very low r ₂/r ₁ ratio (1.98) are developed for high‐contrast T ₁‐weighted MRI of tumors. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay and histological analyses show good biocompatibility of FeGd‐HN3‐RGD2. Laser scanning confocal microscopy images and flow cytometry demonstrate active targeting to integrin α_vβ₃ positive tumors. MRI of tumors shows high tumor ΔSNR for FeGd‐HN3‐RGD2 (477 ± 44%), which is about 6‐7‐fold higher than that of Magnevist (75 ± 11%). MRI and inductively coupled plasma results further confirm that the accumulation of FeGd‐HN3‐RGD2 in tumors is higher than liver and spleen due to the RGD2 targeting and small hydrodynamic particle size (8.5 nm), and FeGd‐HN3‐RGD2 is readily cleared from the body by renal excretion.