Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

Dye-sensitized solar cells (DSCs) offer the possibilities to design solar cells with a large flexibility in shape, color, and transparency. DSC research groups have been established around the worl ...

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Dye-Sensitized Solar Cells

J. Appl. Cryst.の発刊に際して

The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.

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Reticular synthesis and the design of new materials

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.

http://science.sciencemag.org/content/sci/272/5262/704.full.pdf

Photoinduced Magnetization of a Cobalt-Iron Cyanide

The magnetic properties of many magnetic materials can be controlled by external stimuli. The principal focus here is on the thermal, photochemical, electrochemical, and chemical control of phase transitions that involve changes in magnetization. The molecular compounds described herein range from metal complexes, through pure organic compounds to composite materials. Most of the Review is devoted to the properties of valence-tautomeric compounds, molecular magnets, and spin-crossover complexes, which could find future application in memory devices or optical switches.

Control of magnetic properties through external stimuli.

The development of molecular materials whose physical properties can be controlled by external stimuli - such as light, electric field, temperature, and pressure - has recently attracted much attention owing to their potential applications in molecular devices. There are a number of ways to alter the physical properties of crystalline materials. These include the modulation of the spin and redox states of the crystal's components, or the incorporation within the crystalline lattice of tunable molecules that exhibit stimuli-induced changes in their molecular structure. A switching behaviour can also be induced by changing the molecular orientation of the crystal's components, even in cases where the overall molecular structure is not affected. Controlling intermolecular interactions within a molecular material is also an effective tool to modulate its physical properties. This Review discusses recent advances in the development of such stimuli-responsive, switchable crystalline compounds - referred to here as dynamic molecular crystals - and suggests how different approaches can serve to prepare functional materials.

Dynamic molecular crystals with switchable physical properties

Molecular-based ferrimagnetic thin films with high critical temperatures (Tc) composed of mixed-valence chromium cyanides were synthesized by means of a simple electrochemical route. The highest Tc was 270 K, obtained for Cr2.12(CN)6. The Tc values were easily controlled by changing the preparation conditions. Moreover, a reversible shift of Tc could be electrochemically induced. As a result of such electrochemical control, these cyanides can be switched reversibly back and forth between ferrimagnetism and paramagnetism. These magnets thus represent materials in which magnetic properties are combined with electrical functions.

http://science.sciencemag.org/content/sci/271/5245/49.full.pdf

Electrochemically Tunable Magnetic Phase Transition in a High-Tc Chromium Cyanide Thin Film

The study of biological microstructure is one of the most important research areas in biomimicry.[1–3] Microstructure plays many important roles in living things.[2,3] For example, the charming blue color of the Morpho sulkowskyi butterfly originates from light diffraction and scattering, which results from the ordered microstructure of its scales. This form of color is usually known as structural color, which is utilized by animals both for protection and as a warning. Today, the study of structural color has been extended from biology to optics.[4–6] As well as affecting coloration, microstructure also plays an important role in self-cleaning.[2, 7] For the butterfly, the specific nanostructure enhances the hydrophobicity of its wings, which allows droplets of water to be dispersed more easily. During this process, dust particles on the surface of the wings are removed. This phenomenon is known as the “lotus effect”, which is not only very useful for natural species, but also for materials applications, such as for decoration where a natural force might be used to clean a surface. It would be interesting to discover whether it is possible to design a material that incorporates both structural color and the lotus effect, thus mimicking the wings of a butterfly. Such a material should be of great biological and technological importance. In this paper, we will show one approach to fabricating such a biomimetic decorative material by taking advantage of a nanostructured inverse opal surface. Inverse opal is a solid material that consists of a threedimensional network.[6,8–10] Orderedmonodisperse air spheres throughout the network contribute to an optical stop band, the position of which can be tuned by careful control of the periodicity of the air spheres. Colors can be observed by the naked eye when the stop band falls in the visible region. As a consequence of its unique optical properties, inverse opal has been regarded as a new-generation decorative material, in addition to its application as a photonic crystalline material.[6,11] Recently, we realized that inverse opal might also be incorporated into the design of a hydrophobic material. The solid material network of inverse opal contributes a rough surface composed of well-ordered meshes. According to the Cassie–Baxter law, the intrinsic wettability of the solid material can be greatly reduced.[12] Such a decorative material, which exhibits both structural color and the lotus effect, would be environmentally friendly and energy-efficient. For practical applications, a convenient method of fabricating a uniform inverse opal film over a large area is required. In addition, the rough inverse opal surface needs to be further optimized to imbue the surface with superhydrophobic character. We describe here the development of a dipping method that can be used to meet these criteria, and which can derive uniform inverse opal films with a nanostructured surface. The procedure for the fabrication is as follows: First, submicron-sized monodisperse polystyrene spheres and nanosized particles were ultrasonically dispersed into deionised water. A glass substrate was then immersed into the solution and withdrawn at a constant speed. It is known that a mixture of spheres with different sizes cannot be used to fabricate colloidal crystals with long-range structural order by such a deposition method,[13–15] as phase separation occurs, or an amorphous structure is formed. In our experiment, we found that this conclusion is only partially correct. A structure with long-range order can be derived when the ratio of the diameters of the spheres falls into a particular regime. Figure 1a shows an image of a structure composed of monodisperse spheres, while Figure 1b–d displays three images of structures composed of spheres of two sizes, with diameter ratios of 0.94, 0.34, and 0.07, respectively. The structure formed by the spheres of varying size depends on the diameter ratio. A structure with long-range order can be observed in films composed of monodisperse spheres, however, such order is absent in films composed of spheres of two sizes, where the diameter ratio is larger than 0.15. Usually, the particles form a structure with discernible separation when the ratio between the two types of sphere is larger than 0.5 (Figure 1b), while the domains formed by different types of particles are separated when the ratio is smaller than this value (Figure 1c). When the diameter ratio between the [7] W. P. Rothwell, W. Shen, J. H. Lunsford, J. Am. Chem. Soc. 1984, 106, 2452 – 2453. [8] Each unit cell of CHA contains 36 T sites and three cages. The HSAPO-34 used has one Si, five P, and six Al atoms per cage. [9] J. F. Haw, P. W. Goguen, T. Xu, T. W. Skloss, W. Song, Z. Wang, Angew. Chem. 1998, 110, 993 – 995; Angew. Chem. Int. Ed. 1998, 37, 948 – 949.

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/anie.200390235

Osamu Sato

Papers

Photoinduced Magnetization of a Cobalt-Iron Cyanide

Control of magnetic properties through external stimuli.

Dynamic molecular crystals with switchable physical properties

Electrochemically Tunable Magnetic Phase Transition in a High-Tc Chromium Cyanide Thin Film

Structural color and the lotus effect.