Spin Crossover Nanomaterials: From Fundamental Concepts to Devices
TL;DR: In this progress report, a brief overview on the current state-of-the-art of experimental and theoretical studies of nanomaterials displaying spin transition is presented, and detailed analysis and discussions in terms of finite size effects and other phenomena inherent to the reduced size scale are provided.
Abstract: Nanoscale spin crossover materials capable of undergoing reversible switching between two electronic configurations with markedly different physical properties are excellent candidates for various technological applications. In particular, they can serve as active materials for storing and processing information in photonic, mechanical, electronic, and spintronic devices as well as for transducing different forms of energy in sensors and actuators. In this progress report, a brief overview on the current state-of-the-art of experimental and theoretical studies of nanomaterials displaying spin transition is presented. Based on these results, a detailed analysis and discussions in terms of finite size effects and other phenomena inherent to the reduced size scale are provided. Finally, recent research devices using spin crossover complexes are highlighted, emphasizing both challenges and prospects.
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TL;DR: The field of molecular magnetism is rapidly evolving towards the use of magnetic molecules and molecule-based magnetic materials in physics-driven and nanotechnology-driven fields, in particular molecular spintronics, quantum technologies, metal-organic frameworks (MOFs) and 2D materials as discussed by the authors.
Abstract: The field of molecular magnetism is rapidly evolving towards the use of magnetic molecules and molecule-based magnetic materials in physics-driven and nanotechnology-driven fields, in particular molecular spintronics, quantum technologies, metal–organic frameworks (MOFs) and 2D materials. In molecular spintronics, the goal is the development of a new generation of spintronic devices based on molecular materials or, in the longer term, on one or a few molecules. In the area of quantum technologies, the milestones reached in the design of molecular spin qubits with long quantum coherence times and in the implementation of quantum operations have raised expectations for the use of molecular spin qubits in quantum computation. MOFs and 2D materials are two classes of materials for which magnetism has been, until very recently, an elusive property; molecular materials with attractive properties and functionalities are now starting to be developed in both areas. In MOFs, single-molecule magnets and spin crossover complexes can be integrated into the nodes of the framework, within the pores or both, sometimes giving rise to smart magnetic materials or to hybrid materials exhibiting synergistic combinations of properties. 2D molecular-based magnets can provide a platform to study magnetism in the 2D limit and exhibit superior properties compared with their inorganic analogues in terms of chemical stability and tunability. This Review discusses the expansion of the field of molecular magnetism from the chemical design and physical study of single-molecule magnets and multifunctional magnetic materials towards physics- and nanotechnology-driven areas, in particular molecular spintronics, quantum technologies, metal–organic frameworks and 2D materials.
494 citations
TL;DR: Progress made in the design and synthesis of sublimable functional SCO complexes, on‐surface SCO of molecular and multilayer thick films, and various molecular and thin‐film device architectures based on the sublimably SCO complex are provided.
Abstract: Spin-crossover (SCO) active transition metal complexes are an important class of switchable molecular materials due to their bistable spin-state switching characteristics at or around room temperature. Vacuum-sublimable SCO complexes are a subclass of SCO complexes suitable for fabricating ultraclean spin-switchable films desirable for applications, especially in molecular electronics/spintronics. Consequently, on-surface SCO of thin-films of sublimable SCO complexes have been studied employing spectroscopy and microscopy techniques, and results of fundamental and technological importance have been obtained. This Review provides complete coverage of advances made in the field of vacuum-sublimable SCO complexes: progress made in the design and synthesis of sublimable functional SCO complexes, on-surface SCO of molecular and multilayer thick films, and various molecular and thin-film device architectures based on the sublimable SCO complexes.
132 citations
TL;DR: Recent progress in utilizing MMCT units as actuators to tune magnetic, electric, thermal expansion, and photochromic properties in cyanide-bridged systems is highlighted, and emphasis is given to the remaining challenges and future perspectives in the field.
Abstract: Metal-to-metal charge transfer (MMCT) describes electron transfer between metal ions, to generate valence isomers with markedly different electronic configurations. In particular, MMCT changes the spin states of single-metal sites and the coupling interactions between them, while also changing the symmetry in charge distribution. The result is a drastic change in both magnetic and electric properties of the affected material. Moreover, MMCT causes significant variation in bond length and absorption spectra, and induces unusual thermal expansion and photochromic behavior. Thus, materials demonstrating MMCT in response to external stimuli are excellent candidates for switchable multifunctional devices with synergistic responses. In this Minireview, recent progress in utilizing MMCT units as actuators to tune magnetic, electric, thermal expansion, and photochromic properties in cyanide-bridged systems is highlighted, and emphasis is given to the remaining challenges and future perspectives in the field.
108 citations
TL;DR: This review aims to summarise the chemical strategies that have guided the design of conductive metal-organic frameworks and the identified opportunities for further development and showcase relevant examples of functional devices that have received increasing attention from researchers.
Abstract: Materials scientists are currently shifting from purely inorganic, organic and silicon-based materials towards hybrid organic-inorganic materials to develop increasingly complex and powerful electronic devices. In this context, it is undeniable that conductive metal-organic frameworks (MOFs) and bistable coordination polymers (CPs) are carving a niche for themselves in the electronics world. The tunability and processability of these materials alongside the combination of electrical conductivity with porosity or spin transition offers unprecedented technological opportunities for their integration into functional devices. This review aims to summarise the chemical strategies that have guided the design of this type of materials and the identified opportunities for further development. We also examine the strategies to process them as thin films and stress the importance of analysing the effects of nanostructuration on their physical properties that might be crucial for device performance. Finally, we showcase relevant examples of functional devices that have received increasing attention from researchers and highlight the opportunities available for more sophisticated applications that could take full advantage of the combination of electrical conductivity and magnetic bistability.
101 citations
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TL;DR: In this article, the authors focus on the properties of quantum dots and their ability to join the dots into complex assemblies creates many opportunities for scientific discovery, such as the ability of joining the dots to complex assemblies.
Abstract: Current research into semiconductor clusters is focused on the properties of quantum dots-fragments of semiconductor consisting of hundreds to many thousands of atoms-with the bulk bonding geometry and with surface states eliminated by enclosure in a material that has a larger band gap. Quantum dots exhibit strongly size-dependent optical and electrical properties. The ability to join the dots into complex assemblies creates many opportunities for scientific discovery.
10,737 citations
TL;DR: In this article, the melting points of small gold particles have been measured using a scanning electron-diffraction technique and the experimental results are quantitatively in good agreement with two phenomenological models.
Abstract: Recently, small particles have been shown to exhibit a melting temperature which depends on the particle size. The various possible experimental methods have been compared and measurements of the melting points of small gold particles have been made using a scanning electron-diffraction technique. This method was applied to particles having diameters down to 20 \AA{}. Consideration of the size distribution over an entire sample makes it necessary to carry out a careful analysis of the experimental results in order to deduce the melting temperature of particles having a well-defined diameter. The experimental results are quantitatively in good agreement with two phenomenological models. The first model describes the equilibrium condition for a system formed by a solid particle, a liquid particle having the same mass, and their saturating vapor phase. The second model assumes the preexistence of a liquid layer surrounding the solid particle and describes the equilibrium of such a system in the presence of the vapor phase. In order to permit a better comparison between both models, a new expression for the thermodynamic equilibrium condition has been derived in the present work. In the case of the first model, the agreement was obtained using only the physical constants of massive gold. In applying the second model, however, one is compelled to assume the existence of a liquid layer having a thickness of about 6 \AA{}.
3,074 citations
TL;DR: In this article, the transition temperature of transition metal compounds can be fine tuned using an approach based on the concept of a molecular alloy, and it is possible to design a compound for which room temperature falls in the middle of the thermal hysteresis loop.
Abstract: Some 3dn (4 ≤ n ≤ 7) transition metal compounds exhibit a cooperative transition between a low-spin (LS) and a high-spin (HS) state. This transition is abrupt and occurs with a thermal hysteresis, which confers a memory effect on the system. The intersite interactions and thus the cooperativity are magnified in polymeric compounds such as [Fe(Rtrz)3]A2·nH2O in which the Fe2+ ions are triply bridged by 4-R-substituted-1,2,4-triazole molecules. Moreover, in these compounds, the spin transition is accompanied by a well-pronounced change of color between violet in the LS state and white in the HS state. The transition temperatures of these materials can be fine tuned, using an approach based on the concept of a molecular alloy. In particular, it is possible to design a compound for which room temperature falls in the middle of the thermal hysteresis loop. These materials have many potential applications, for example, as temperature sensors, as active elements of various types of displays, and in information storage and retrieval.
1,934 citations
TL;DR: The light-induced excited spin state trapping (LIESST) as mentioned in this paper phenomenon is well understood within the theoretical context of radiationless transitions and applications of the LIESST effect in optical information technology can be envisaged.
Abstract: Transition metal chemistry contains a class of complex compounds for which the spin state of the central atom changes from high spin to low spin when the temperature is lowered. This is accompanied by changes of the magnetic and optical properties that make the thermally induced spin transition (also called spin crossover) easy to follow. The phenomenon is found in the solid state as well as in solution. Amongst this class, iron(II) spin crossover compounds are distinguished for their great variety of spin transition behavior; it can be anything from gradual to abrupt, stepwise, or with hysteresis effects. Many examples have been thoroughly studied by Mossbauer and optical spectroscopy, measurements of the magnetic susceptibilities and the heat capacities, as well as crystal structure analysis. Cooperative interactions between the complex molecules can be satisfactorily explained from changes in the elastic properties during the spin transition, that is, from changes in molecular structure and volume. Our investigations of iron(II) spin crossover compounds have shown that green light will switch the low spin state to the high spin state, which then can have a virtually unlimited lifetime at low temperatures (this phenomenom is termed light-induced excited spin state trapping - acronym: LIESST). Red light will switch the metastable high spin state back to the low spin state. We have elucidated the mechanism of the LIESST effect and studied the deactivation kinetics in detail. It is now well understood within the theoretical context of radiationless transitions. Applications of the LIESST effect in optical information technology can be envisaged.
1,796 citations
TL;DR: The magnetization in the ferrimagnetic region below 16 kelvin was substantially increased after illumination and could be restored almost to its original level by thermal treatment and these effects are thought to be caused by an internal photochemical redox reaction.
Abstract: Photoinduced magnetization was observed in a Prussian blue analog, K0.2Co1.4- [Fe(CN)6]·6.9H2O. An increase in the critical temperature from 16 to 19 kelvin was observed as a result of red light illumination. Moreover, the magnetization in the ferrimagnetic region below 16 kelvin was substantially increased after illumination and could be restored almost to its original level by thermal treatment. These effects are thought to be caused by an internal photochemical redox reaction. Furthermore, blue light illumination could be used to partly remove the enhancement of the magnetization. Such control over magnetic properties by optical stimuli may have application in magneto-optical devices.
1,537 citations