Kunio Awaga

Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound

Progress in metal–organic framework (MOF) research has recently opened up new possibilities to realize hybrid materials with unique solid-state electric properties, such as ferroelectricity, piezoelectricity, and dielectricity. Compared with conventional pure inorganic/organic compounds, MOFs take advantage of structural tunability and multifunctionality to develop polarizable molecular materials with rich dielectric properties. Among them, switchable molecular dielectrics, which undergo transitions between high and low dielectric states, are promising materials with potential applications especially in data communication, signal processing, and sensing. However, reports of such MOFs have remained scarce owing to a lack of knowledge regarding control of the motions of the dipole moments in the crystal lattice. From the microscopic point of view, the tunable dielectric permittivity closely relates to the positional freedom of molecular dipole moments. For instance, polar molecules in the liquid state show larger dielectric permittivities than in the solid state owing to the “melting” and “freezing” of the molecular reorientations. With regard to MOFs, the dipole moments are rigidly fixed in the crystal structures in most cases, usually resulting in small and almost temperatureindependent dielectric permittivities. Fortunately, there is still much room for the integration of flexible units into the frameworks; that is, the introduction of a polarization rotation unit in the form of a solid-state molecular rotator or host–guest systems, such as porous compounds. Cage compounds, which are assembled by the inclusion of guest species into the well-matched host cages, is a very promising class of switchable molecular dielectrics. The reorientations of the polar guests in the carefully designed cage compounds may give rise to large dielectric permittivities, which are characterized by a multidimensional liquidlike state, and their freezing will lead to low-dielectric systems. Herein, we present a novel organic–inorganic hybrid cage compound (HIm)2[KFe(CN)6] (1; HIm = imidazolium) with a perovskite-type structure, in which the order– disorder behavior of the HIm polar guests give rise to striking dielectric anomalies. The (HIm)2[KFe(CN)6] crystals were grown from an aqueous solution of K3[Fe(CN)6] and (HIm)Cl salts by slow evaporation at room temperature as large red hexagonal plate perpendicular to the c axis. The existence of HIm and CN groups in 1 is verified by IR spectra. The CN group in 1 exhibits several vibrations in the range 2102–2143 cm , distinct from a single peak of 2118 cm 1 in K3[Fe(CN)6]. Thermal analysis reveals that 1 undergoes two phase transitions, at 187 K (T1) and 158 K (T2). For convenience, we label the phase above T1 as the high-temperature phase (HTP), the phase between T1 and T2 as intermediate-temperature phase (ITP), and the phase below T2 as low-temperature phase (LTP). Variable-temperature X-ray diffraction analysis reveals that 1 crystallizes in the centrosymmetric space group R3̄m at 293 K and 173 K as the HTP and ITP, respectively, and in C2/c at 83 K as the LTP. The common structural feature of the compound is the anionic cage formed by Fe CN K units in which the HIm cation resides. The metal–cyanide bond is strong and covalent in the fragment {Fe(CN)6} (Fe C = 1.9 ) and much weaker and ionic in the fragment {K(NC)6} (K N = 2.9 ; Figure 1). In the HTP, the cation reorients around the threefold c axis perpendicular to the ring plane. The cation consists of three carbon and two nitrogen atoms, which were all refined as carbon atoms. The five atoms of the

In Operando X-ray Absorption Fine Structure Studies of Polyoxometalate Molecular Cluster Batteries: Polyoxometalates as Electron Sponges

We carried out in operando Mo K-edge X-ray absorption fine structure measurements on the rechargeable molecular cluster batteries (MCBs) of polyoxometalates (POMs), in which a Keggin-type POM, [PMo(12)O(40)](3-), is utilized as a cathode active material with a lithium metal anode. The POM-MCBs exhibit a large capacity of ca. 270 (A h)/kg in a voltage range between V = 4.0 V and V = 1.5 V. X-ray absorption near-edge structure analyses demonstrate that all 12 Mo(6+) ions in [PMo(12)O(40)](3-) are reduced to Mo(4+) in the discharging process. This means the formation of a super-reduced state of the POM, namely, [PMo(12)O(40)](27-), which stores 24 electrons, and this electron number can explain the large capacity of the POM-MCBs. Furthermore, extended X-ray absorption fine structure analyses reveal the molecular structure of [PMo(12)O(40)](27-), which is slightly reduced in size compared to the original [PMo(12)O(40)](3-) and involves Mo(4+) metal-metal-bonded triangles. Density functional theory calculations suggest that these triangles are formed because of the large number of additional electrons in the super-reduced state.

Electric-double-layer field-effect transistors with ionic liquids

Charge carrier control is a key issue in the development of electronic functions of semiconductive materials. Beyond the simple enhancement of conductivity, high charge carrier accumulation can realize various phenomena, such as chemical reaction, phase transition, magnetic ordering, and superconductivity. Electric double layers (EDLs), formed at solid-electrolyte interfaces, induce extremely large electric fields. This results in a high charge carrier accumulation in the solid, much more effectively than solid dielectric materials. In the present review, we describe recent developments in the field-effect transistors (FETs) with gate dielectrics of ionic liquids, which have attracted much attention due to their wide electrochemical windows, low vapor pressures, and high chemical and physical stability. We explain the capacitance effects of ionic liquids, and describe the various combinations of ionic liquids and organic and inorganic semiconductors that are used to achieve such effects as high transistor performance, insulator-metal transitions, superconductivity, and ferromagnetism, in addition to the applications of the ionic-liquid EDL-FETs in logic devices. We discuss the factors controlling the mobility and threshold voltage in these types of FETs, and show the ionic liquid dependence of the transistor performance.

Ferromagnetic coupling in a new phase of the p-nitrophenyl nitronyl nitroxide radical

Abstract The crystal structure of a new phase of the p -nitrophenyl nitronyl nitroxide radical compound is described. A study of its magnetic properties reveals the largest intermolecular ferromagnetic coupling reported so far among a series of polymorphs of this compound.

Ferromagnetic intermolecular interaction of the organic radical, 2-(4-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1h-imidazolyl-1-oxy 3-oxide

Abstract The temperature dependence of the magnetic susceptibility and the magnetization curve of the organic free radical, 2-(4-nitro-phenyl)-4,4,5,5-tetrameth intermolecular interaction obtains in the crystal of 1 . The Curie and Weiss constants are 0.375 emu K mol −1 and +0.9 K, respectively.

Ferromagnetic intermolecular interaction in the galvinoxyl radical: Cooperation of spin polarization and charge-transfer interaction

Abstract The orbital energies and the intermolecular overlap integrals of the galvinoxyl radical are calculated. It is found that the ferromagnetic intermolecular interaction in galvinoxyl can be qualitatively interpreted by a combined effect of spin polarization within the radical and charge-transfer interaction between the radicals.

Monitoring the solid-state electrochemistry of Cu(2,7-AQDC) (AQDC = anthraquinone dicarboxylate) in a lithium battery: coexistence of metal and ligand redox activities in a metal-organic framework.

By adopting a facile synthetic strategy, we obtained a microporous redox-active metal-organic framework (MOF), namely, Cu(2,7-AQDC) (2,7-H2AQDC = 2,7-anthraquinonedicarboxylic acid) (1), and utilized it as a cathode active material in lithium batteries. With a voltage window of 4.0-1.7 V, both metal clusters and anthraquinone groups in the ligands exhibited reversible redox activity. The valence change of copper cations was clearly evidenced by in situ XANES analysis. By controlling the voltage window of operation, extremely high recyclability of batteries was achieved, suggesting the framework was robust. This MOF is the first example of a porous material showing independent redox activity on both metal cluster nodes and ligand sites.

Ferromagnetic and antiferromagnetic intermolecular interactions of organic radicals, α‐nitronyl nitroxides. II

The temperature dependence of the magnetic susceptibilities and the magnetizations for the three kinds of α‐nitronyl nitroxides, 2‐R‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐oxy 3‐oxide [with R=phenyl (I), 3‐nitrophenyl (II), 4‐nitrophenyl (III)] have been measured. It is found that the intermolecular spin interaction is ferromagnetic in the crystal of III, while it is antiferromagnetic in I or II. UV–visible absorption spectra suggests the enhancements of the π‐electron delocalization and the spin polarization in III in comparison with the others. The difference in the magnetic coupling between I or II and III is interpreted based on these two effects.

Ferromagnetic intermolecular interactions in a series of organic mixed crystals of galvinoxyl radical and its precursory closed shell compound

The magnetic properties of the 4:1, 6:1, 9:1, and 19:1 mixed crystals of galvinoxyl (4‐[[3,5‐bis(1,1‐dimethylethyl)‐4‐oxo‐2,5‐cyclohexadien‐1‐ylidene]methyl]‐2,6 ‐bis(1,1‐dimethylethyl) phenoxy) radical and its precursory closed shell compound, hydrogalvinoxyl, have been studied. From the measurements of the temperature dependence of the magnetic susceptibility, it is found that the ferromagnetic intermolecular interactions, which are lost below about 85 K in pure galvinoxyl because of the phase transition, are maintained down to 2 K in these mixed crystals, and that the number of galvinoxyl radicals keeping the ferromagnetically coupled structure at low temperature increases as the concentration of hydrogalvinoxyl increases. The magnetic behavior of the mixed crystals at low temperature depends on the thermal history of the sample and is well interpreted by assuming the presence of a glassy state into which the high‐temperature, ferromagnetically coupled phase is quenched. The magnetization curves show t...

Preparation and magnetic properties of hollow nano-spheres of cobalt and cobalt oxide: Drastic cooling-field effects on remnant magnetization of antiferromagnet

We investigate the making of magnetic hollow spheres of Co3O4 (2) and fcc Co (3) with diameter 500 nm and thickness 40 nm, using polystyrene-bead templates. The spheres are characterized by scanning electron microscope, transmission electron microscope, electron diffraction, and x-ray diffraction. Magnetic measurements on 2 reveal a drastic enhancement of remnant magnetization below TN induced by cooling-field, while measurements on 3 indicate a soft ferromagnetism similar to that of bulk fcc Co.