論文

Dihydroquinazoline FeII complexes, namely [Fe(pq-R)(2)](X)(2)center dot CH3OH center dot yCH(3)CN center dot zH(2)O (R = 2-py: X = ClO4-, x = 1, y = 0, z = 2 (1), BF4-, x = 0, y = 2, z = 1.75 (2), CF3SO3-, x = 1, y = 1, z = 0 (3); and X = ClO4-: R = 2-OCH3, x = 0, y = 0, z = 1 (4), R = 3-OCH3, x = 0, y = 0, z = 1 (5)), were prepared and the effects of the solvent, counteranion and ligand substituent on spin crossover properties were discussed. Comparison of X-ray diffraction data for these complexes revealed the sole presence of high-spin FeII at 298 K and the bond distances around the FeII center at low temperature fall much closer to those at high temperature, which is consistent with variable-temperature dc magnetic susceptibility data. However, the loss of solvent induced a significant change in the spin state of complexes 1 and 2. Moreover, fits to magnetic data of the desolvated samples provide crossover temperatures of T-1/2 = 182.9(6), 157.0(8) and 138.3(5) K for 1-des (ClO4-), 2-des (BF4-) and 3-des (CF3SO3-), respectively, indicative of the anion-dependent transition temperature. The cooperativity operating in the complexes is thought to be mainly from the intermolecular pi center dot center dot center dot pi interactions between dihydroquinazoline rings on the neighboring molecules. The ligand substituent effect was also investigated on Fe-II SCO properties. This work revealed the spin crossover properties of new types of dihydroquinazoline Fe(II) complexes, including the transition temperature, the degree of completion and the cooperative nature of the transition, which can be optimally designed when developing new spin-crossover materials.

Co-Fe Prussian blue thin films have been prepared by means of a modified Langmuir-Blodgett technique, in which the hybrid monolayer composed of amphiphiles and clay platelets plays a template role for the formation Co-Fe Prussian blue thin films. Photoinduced magnetization was observed in the thin films as observed in the bulk Co-Fe Prussian blue. To the best of our knowledge, this is the first example Of Successful formation of Co-Fe Prussian blue thin films, which possess the ordered structure and, in addition, exhibit photoinduced magnetization.

A novel photocontrollable magnetic thin film consisting of amphiphilic azobenzene cations, a smectite clay, and Prussian Blue has been designed and prepared by using the Langmuir-Blodgett method and an ion-exchange reaction. This magnetic thin film possesses a well-organized nanoscale layered structure. Reversible photoisomerization of the azobenzene chromophore realized photoswitching of the magnetization. The changes in the magnetization values were estimated to be ca. 11%. This figure was much larger than our previous system, which contained azobenzene multi-bilayered vesicles in a poly(vinyl alcohol) matrix (J. Am. Chem. Soc. 1999, 121, 3745). These larger changes in the magnetization values are due to the highly ordered structure of the hybrid multilayered films.

A key issue in molecular electronics is the control of electronic states by optical stimuli, which enables fast and high-density data storage and temporal-spatial control over molecular processes. In this article, we report preparation of a photoswitchable superconductor using a heavily boron-doped diamond (BDD) with a photochromic azobenzene (AZ) molecular layer. BDDs electrode properties allow for electrochemical immobilization, followed by copper(I)-catalyzed alkyne-azide cycloaddition (a click reaction). Superconducting properties were examined with magnetic and electrical transport measurements, such as field-dependent isothermal magnetization, temperature-dependent resistance, and the low-temperature voltage-current response. These measurements revealed reversible amplification of the critical current density by 55% upon photoisomerization. This effect is explained as the reversible photoisomerization of AZ inducing an inhomogeneous electron distribution along the BDD surface that renormalizes the surface pinning contribution to the critical current.

Fe-57 Mossbauer spectroscopy was applied to an iron-based layered compound CeFePO. At temperatures from 9.4 to 293 K, no magnetic splitting was observed in the Mossbauer spectra of CeFePO indicating a paramagnetic phase of the Fe magnetic sublattice. All the spectra were fitted with a small quadrupole splitting, and the Debye temperature of CeFePO was found to be similar to 448 K. The isomer shift at room temperature, 0.32 mm/s, was almost equal to those of LnFeAsO (Ln = La, Ce, Sm). Comparing s-electron density using the isomer shifts and unit cell volumes, it was found that the Fe of CeFePO has a similar valence state to other layered iron-based quaternary oxypnictides except LaFePO.

Magnetically bistable solid solutions of Prussian blue analogues with chemical formulas of KaNi1-xCox[Fe(CN)(6)](beta)center dot nH(2)O (Ni1-xCoxFe) and K alpha Co gamma[Fe(CN)(6)](y)[Cr(CN)(6)](1-y)center dot nH(2)O (CoFeyCr1-y) have been synthesized and studied using mass spectrometry, Mossbauer spectroscopy, X-ray diffraction, temperature-dependent infrared spectroscopy, and dc magnetometry. These compounds provide insight into interfaces between the photomagnetic Co-Fe Prussian blue analogue and the high-T-C Ni-Cr Prussian blue analogue that exist in high-T-C photomagnetic heterostructures. This investigation shows that the bistability of Co-Fe is strongly modified by metal substitution, with Ni1-xCoxFe stabilizing high-spin cobalt-iron pairs and CoFeyCr1-y stabilizing low-spin cobalt iron pairs, while both types of substitution cause a dramatic decrease in the bistability of the material.

Ultrathin fims composed of titania nanosheets and Prussian Blue were prepared by using the modified Langmuir-Blodgett technique. The ultrathin films could be deposited in a layer-by-layer manner with lamellar structure. Upon band gap excitation of titania nanosheets, the generated electrons were injected into ferromagnetic Prussian Blue, resulting in reduction to paramagnetic Prussian White. It was revealed that the reaction could proceed only in the presence of hole-scavenging interlayer water molecules.

Two novel types of photomagnetic hybrid ultrathin film (film A and B) of metal cyanides have been fabricated by means of the modified Langmuir-Blodgett method using a smectite clay mineral. Film A is composed of an amphiphilic azobenzene cation, a montmorillonite, and Prussian Blue in which photocontrol in the magnetization was realized by the photoisomerization of azobenzene chromophore. The observed photomagnetic efficiency was large (ca. 11%) due to the well-organized structure of the ultrathin film. Film B is composed of a quaternary ammonium salt, a montmorillonite, and Co-Fe Prussian Blue in which the photoinduced magnetization caused by the electron transfer exhibited an anisotropic response with regards to the direction of the applied magnetic field. This phenomenon is ascribed to the unique structure of Co-Fe Prussian Blue formed onto the clay layer.

A photomagnetic ultrathin film consisting of an azobenzene, a deoxyribonucleic acid, and Prussian Blue has been fabricated by the Langmuir-Blodgett method. Prussian Blue layers in the films were a two-dimensional structure with the height of 50 A and the average coherence length of 210 A. Reversible photoisomerization of the azobenzenes was observed even in the films. The films exhibit the long-range ferromagnetic order below 4.2 K and moreover, upon photoillumination at 2 K, reversible changes in the magnetization were realized with the value of ca. 1.0%. This photoswitching in the magnetization is due to changes in the electrostatic field induced by photoisomerization. (C) 2007 Elsevier B.V. All rights reserved.

A photomagnetic organized thin film consisting of an amphiphilic azobenzene, a smectite clay, and Prussian Blue has been prepared by utilizing the Langmuir-Blodgett (LB) method and an ion-exchange reaction. The magnetic LB films were revealed to possess an organized layered structure, and reversible photoisomerization of the azobenzene was observed even in the LB films. Upon photoillumination at 2 K, reversible changes in the magnetization were realized with the value of ca. 11%. This photoswitching in the magnetization is due to changes in the electrostatic field induced by photoisomerization of the azobenzene. A large photoinduced change in the magnetization would be owing to the highly ordered structure of the LB films. In order to verify the correlation between the film structure and photoswitching efficiency, the LB films have been fabricated in other condition. As results, it is confirmed that the packing state of the azobenzene plays an important and crucial role in accomplishment of the highly efficient photomagnetic switching. (c) 2006 Elsevier Ltd. All rights reserved.

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim An oxidative cleavage reaction of the acyl−carbon bond in phenylacetone derivatives under cathodic reduction is reported. This particular transformation is driven by the cathodic reduction of dissolved molecular oxygen to superoxide anions. Various cathode materials were examined, and we discovered that boron-doped diamond (BDD) enables highly efficient molecular conversion, owing to BDD's outstanding electrochemical property for utilizing the small amounts of molecular oxygen effectively. The scope of the reaction is broad and can be applied to a variety of substrates, ranging from ketones to esters and amides. As an electric current is directly employed to generate the superoxide anion, the reaction is metal- and catalyst-free. Electro-organic synthesis using the carbon-based BDD electrode thus provides access to sustainable molecular transformations.

In this chapter, photo-modulation of superconducting and magnetic properties is described. First, the superconducting property of a boron-doped diamond is investigated, in which the critical current density varies dramatically between the hydrogen- and oxygen-terminated diamond. Second, the superconducting diamond is modified with an azobenzene molecular layer to modulate the superconductivity upon photoirradiation. In this composite superconductor, the critical current density is reversibly amplified by 55% upon photoisomerization of the azobenzene layer. Third, Prussian Blue, a coordination polymer, is integrated with the semiconducting titanium oxide nanosheets to modulate the magnetic property upon photoirradiation. In this magnetic heterostructure, photoinduced magnetic phase transition of Prussian Blue is present by injecting photoexcited electrons from titanium oxide nanosheets.

Thin films of cobalt-iron cyanide (Co-Fe Prussian blue) have been fabricated by means of the modified Langmuir-Blodgett (LB) method using a smectite clay mineral (montmorillonite). In this combined method, clay LB films play a template role in the formation of the Co-Fe Prussian blue thin layer. The films were revealed to possess a well-organized structure not only in perpendicular directions to the film surface but also in parallel directions to the film surface. The photoinduced electron transfer from the iron ion to the cobalt through the bridging cyanide in the films occurred at low temperature (8 K), similar to that in the bulk Co-Fe Prussian blue. The films clearly exhibited magnetic anisotropy with regards to the direction of the applied magnetic field. Moreover, the photoinduced magnetization effect in the films was also found to be anisotropic.

The maximum current flowed with zero resistance, referred to the critical current density, is desired to be sufficiently large in order to apply superconducting wire rods and electromagnets to various devices. Although the critical current density can be enhanced by introduction of non-superconducting impurities, the transition temperature would become diminished in such a case. Here, we report modulation of a critical current density in heavily boron-doped diamonds (BDDs) by changing the surface-termination without introducing any impurity. The surface of a BDD was changed between hydrogen- and oxygen-termination. As a result, the critical current density could be modulated in a reversible manner between the hydrogen- and oxygen-terminated diamonds with maintenance of the superconducting transition temperature. This is because the volume fractions of the superconducting phases were modulated by surface modification. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spiropyran-montmorillonitehybrid materials have been fabricated by the Langmuir-Blodgett(LB) and an intercalation method. The LB method using clay minerals could be applied to fabricate hybrid ultrathin films consisting of a non-amphiphilic spiropyran. It is confirmed that hybrid LB films possess the layered structure and exhibit "normal photochromism" without any changes in the layered structure. In case of the intercalation method, hybrid compounds also possess the layered structure. Interestingly, intercalation hybrid compounds exhibit "reverse photochromism". It is suggested that a different process in formation of the layered structure influences the observed photochromism. (C) 2007 Elsevier B.V. All rights reserved.

© 2018 American Association for the Advancement of Science. All rights reserved. In heterostructures with broken inversion symmetry, the electrons' motion is coupled to their spin through interface-driven spin-orbit coupling: the Rashba effect. The Rashba effect enables the interconversion between spin and charge currents, offering a variety of novel spintronic phenomena and functionalities. However, despite the significant progress in Rashba physics, controlling the spin-charge conversion in metallic heterostructures remains a major challenge. We show that molecular self-assembly provides a way to engineer the Rashba spin-charge converters. We demonstrate that magnetoresistance and voltage generation originating from the spin-charge conversion in metallic heterostructures can be manipulated by decorating the surface with selfassembled organic monolayers through the cooperative molecular field effect. We also demonstrate reversible phototuning of the spin-charge conversion through light-driven molecular transformations using a molecule that can photoisomerize between the trans and cis states. These findings, with the almost-infinite chemical tunability of organic monolayers, pave the way toward molecular engineering of spin-orbit devices.

To introduce both an inter-sulphur atom and p-stacking interaction between a spin crossover (SCO) cation and paramagnetic anion, we designed and synthesised two novel Fe(II) SCO compounds involving a terpyridine-type thiazole containing ligand with the paramagnetic Ni(dmit)(2) and nonmagnetic Au(dmit)(2) anion (dmit = 4,5-dithiolato-1,3-dithiole-2-thione). The temperature variations of magnetic susceptibility and Mossbauer spectroscopy revealed that both complexes exhibited an almost complete SCO conversion, and moreover, the Ni(dmit)(2) anion was in a paramagnetic state down to 2 K. The crystal structures for the Ni(dmit)(2) complex at 213 and 400 K indicated that the chalcogen-bond and p-stacking interaction would be enhanced by the electrostatic interaction between the cation and anion, preventing the p-radicals from dimerising. The light-induced excited spin state trapping effect was observed at 5 K.

An important technique to realize novel electron- and/or proton-based functionalities is to use a proton-electron coupling mechanism. When either a proton or electron is excited, the other one is modulated, producing synergistic functions. However, although compounds with proton-coupled electron transfer have been synthesized, crystalline molecular compounds that exhibit proton-transfer-coupled spin-transition (PCST) behavior have not been reported. Here, we report the first example of a PCST Fe(II) complex, wherein the proton lies on the N of hydrazone and pyridine moieties in the ligand at high-spin and low-spin Fe(II), respectively. When the Fe(II) complex is irradiated with light, intramolecular proton transfer occurs from pyridine to hydrazone in conjunction with the photoinduced spin transition via the PCST mechanism. Because the light-induced excited high-spin state is trapped at low temperatures in the Fe(II) complex-a phenomenon known as the light-induced excited-spin-state trapping effect-the light-induced proton-transfer state, wherein the proton lies on the N of hydrazone, is also trapped as a metastable state. The proton transfer was accomplished within 50 ps at 190 K. The bistable nature of the proton position, where the position can be switched by light irradiation, is useful for modulating proton-based functionalities in molecular devices.

Langmuir-Blodgett methods are perhaps the original approach for achieving controlled deposition of organic thin films. Molecules are first organized into a monolayer array on the surface of water before transfer as a monolayer onto solid supports. Molecular monolayers, multilayers, and multilayered heterostructures can be achieved. The capability of exercising such control over thin film assemblies has attracted materials chemists and physicists to develop Langmuir-Blodgett films for studies on organic conductors, magnets, non-linear optics, rectifiers, and intermolecular electron transfer. This article reviews objectives in each of these areas and selects some specific examples from the literature to highlight the state of the art, mostly from the point of view of the chemical systems that are studied. Mixed organic/inorganic hybrid films represent a new direction for Langmuir-Blodgett films in materials science, combining conventional inorganic solid-state phenomena with the properties of the organic networks, and recent examples, taken principally from the authors' work, are highlighted.

© 2019 American Chemical Society. Carbon-based materials are regarded as an environmentally benign alternative to the conventional metal electrode used in electrochemistry from the viewpoint of sustainable chemistry. Among various carbon electrode materials, boron-doped diamond (BDD) exhibits superior electrochemical properties. However, it is still uncertain how surface chemical species of BDD influence the electrochemical performance, because of the difficulty in characterizing the surface species. Here, we have developed in situ spectroscopic measurement systems on BDD electrodes, i.e., in situ attenuated total reflection infrared spectroscopy (ATR-IR) and electrochemical X-ray photoelectron spectroscopy (EC-XPS). ATR-IR studies at a controlled electrode potential confirmed selective surface hydroxylation. EC-XPS studies confirmed deprotonation of C-OH groups at the BDD/electrolyte interface. These findings should be important not only for better understanding of BDD's fundamentals but also for a variety of applications.