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.

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.

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.

The electronic and spin states of a series of Co-Fe Prussian blue analogues containing Na(+) ion in the lattice, Na(x)()Co(y)()Fe(CN)(6) x zH(2)O, strongly depended on the atomic composition ratio of Co to Fe (Co/Fe) and temperature. Compounds of Co/Fe = 1.5 and 1.15 consisted mostly of the Fe(III)(t(2g)(5)e(g)(0), LS, S = 1/2)-CN-Co(II)(t(2g)(5)e(g)(2), HS, S = 3/2) site and the Fe(II)(t(2g)(6)e(g)(0), LS, S = 0)-CN-Co(III)(t(2g)(6)e(g)(0), LS, S = 0) site, respectively, over the entire temperature region from 5 to 350 K. Conversely, compounds of Co/Fe = 1.37, 1.32, and 1.26 showed a change in their electronic and spin states depending on the temperature. These compounds consisted mainly of the Fe(III)-CN-Co(II) site (HT phase) around room temperature but turned to the state consisting mainly of the Fe(II)-CN-Co(III) site (LT phase) at low temperatures. This charge-transfer-induced spin transition (CTIST) phenomenon occurred reversibly with a large thermal hysteresis of about 40 K. The CTIST temperature (T(1/2) = (T(1/2) descending + T(1/2) ascending)/2) increased from 200 to 280 K with decreasing Co/Fe from 1.37 to 1.26. Furthermore, by light illumination at 5 K, the LT phase of compounds of Co/Fe = 1.37, 1.32, and 1.26 was converted to the HT phase, and the relaxation temperature from this photoproduced HT phase also strongly depended on the Co/Fe ratio; 145 K for Co/Fe = 1.37, 125 K for Co/Fe = 1.32, and 110 K for Co/Fe = 1.26. All these phenomena are explained by a simple model using potential energy curves of the LT and HT phases. The energy difference of two phases is determined by the ligand field strength around Co(II) ions, which can be controlled by Co/Fe.

Two kinds of cobalt-iron cyanides (Rb(0.66)Co(1.25)[Fe(CN)(6)].4.3H(2)O and Co(1.5)[Fe(CN)(6)].6H(2)O) with different electronic structures have been investigated to understand the photoinduced long-range magnetic ordering. Rb(0.66)Co(1.25)[Fe(CN)(6)].4.3H(2)O produces a photomagnetic effect, whereas Co(1.5)[Fe(CN)(6)].6H(2)O does not respond to light. FT-IR and Mössbauer studies revealed that their oxidation states are expressed as Rb(0.66)Co(III)(0.84)Co(II)(0.41)[Fe(II)(CN)(6)] and Co(II)(1.5)[Fe(III)(CN)(6)], respectively. The difference in the oxidation states of the metal atoms in these two compounds has been explained by the Co coordination with H(2)O or CN ligands. In the case of Rb(0.66)Co(1.25)[Fe(CN)(6)].4.3H(2)O, more CN ligands are involved in coordination than expected in the case of Co(1.5)[Fe(CN)(6)].6H(2)O. A charge-transfer (CT) band from Fe(II) to Co(III) is observed at around 550 nm for Rb(0.66)Co(1.25)[Fe(CN)(6)].4.3H(2)O. The magnetism of Rb(0.66)Co(1.25)[Fe(CN)(6)].4.3H(2)O changed from paramagnetic to ferrimagnetic due to the CT from Fe(II) to Co(III) when illuminated at low temperature. The Curie temperature after illumination was 22 K. This metastable state was stable for more than several days at 5 K. The metastable state was restored back to its original one when the sample was heated to 120 K. It is considered that the interconversion proceeded via a pronounced domain formation.

A dipping method was developed to fabricate three-dimensional colloidal crystal films. The thickness of the films fabricated by this method can be precisely controlled from one layer to several tens of layers by controlling the particle concentration and the film formation speed. Experimental results showed that the spheres form a face-centered cubic structure and that single crystals in the film can extend to centimeter dimensions.

Dry and bright: To mimic the wings of the displayed Morpho butterfly, a new decorative material that exhibits both structural color and superhydrophobicity (the “lotus effect”) was developed by taking advantage of the unique structural properties of an inverse opal film, which was fabricated by the self‐assembly of polystyrene spheres and silica nanoparticles.

Molecular-based ferrimagnetic thin films with high critical temperatures (TJ composed of mixed-valence chromium cyanides were synthesized by means of a simple electrochemical route. The highest Tc was 270 K, obtained for Cr, . , , (CN), .The Tc values were easily controlled by changing the preparation conditions. Moreover, a reversible shift of T , 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.