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The complex containing iron(II), 2,6-bis(pyrazol-3-yl)pyridine (3-bpp) as ligand, and tetracyanonickelate as counter anion has been synthesized and characterized. The characterization data suggest the corresponding formula of [Fe(3-bpp)2][Ni(CN)4]·4H2O. Meanwhile, the SEM–EDX analysis image confirms the existence of all elements contained in the complex except the hydrogen atom. The infrared spectra exhibit vibration bands of the functional groups of 3-bpp ligand and [Ni(CN)4]−1 anion. From magnetic property measurement, the complex's molar magnetic susceptibility (XMT) value is 2.65 emu mol−1 K at 300 K, which contains about 75% high-spin state of the Fe(II) complex. Upon lowering the temperature, the XMT value gradually decreases around 1.37 emu mol−1 K at 13 K. It decreases sharply to about 0.73 emu mol−1 K at 2 K. These values reveal that Fe(II) complex is in the low-spin (LS) state. As a result, the complex exhibited spin-crossover characteristics of gradual transition without thermal hysteresis, and the transition temperature occurred below room temperature with a transition temperature (T1/2) close to 140 K. The spin crossover property of the complex is supported by a thermochromic reversible color change from red-brown at room temperature to dark brown on cooling in liquid nitrogen associated with the high-spin to low-spin transition.

Abstract Exploring new topological phenomena and functionalities induced by strong electron correlation has been a central issue in modern condensed-matter physics. One example is a topological insulator (TI) state and its functionality driven by the Coulomb repulsion rather than a spin-orbit coupling. Here, we report a ‘correlation-driven’ TI state realized in an organic zero-gap system α-(BETS)2I3. The topological surface state and chiral anomaly are observed in temperature and field dependences of resistance, indicating a three-dimensional TI state at low temperatures. Moreover, we observe a topological phase switching between the TI state and non-equilibrium Dirac semimetal state by a dc current, which is a unique functionality of a correlation-driven TI state. Our findings demonstrate that correlation-driven TIs are promising candidates not only for practical electronic devices but also as a field for discovering new topological phenomena and phases.

Abstract Magnetic properties of Mott–Hubbard systems are generally dominated by strong antiferromagnetic interactions produced by the Coulomb repulsion of electrons. Although theoretical possibility of a ferromagnetic ground state has been suggested by Nagaoka and Penn as single-hole doping in a Mott insulator, experimental realization has not been reported more than half century. We report the first experimental possibility of such ferromagnetism in a molecular Mott insulator with an extremely light and homogeneous hole-doping in π-electron layers induced by net polarization of counterions. A series of Ni(dmit)2 anion radical salts with organic cations, where dmit is 1,3-dithiole-2-thione-4,5-dithiolate can form bi-layer structure with polarized cation layers. Heat capacity, magnetization, and ESR measurements substantiated the formation of a bulk ferromagnetic state around 1.0 K with quite soft magnetization versus magnetic field (M–H) characteristics in (Et-4BrT)[Ni(dmit)2]2 where Et-4BrT is ethyl-4-bromothiazolium. The variation of the magnitude of net polarizations by using the difference of counter cations revealed the systematic change of the ground state from antiferromagnetic one to ferromagnetic one. We also report emergence of metallic states through further doping and applying external pressures for this doping induced ferromagnetic state. The realization of ferromagnetic state in Nagaoka–Penn mechanism can paves a way for designing new molecules-based ferromagnets in future.

The Fermi surface structure of a layered organic superconductor β″-(BEDT-TTF)2SF5CH2CF2SO3 was determined by angular-dependent magnetoresistance oscillations measurements and band-structure calculations. This salt was found to have two small pockets with the same area: a deformed square hole pocket and an elliptic electron pocket. Characteristic corrugations in the field dependence of the interlayer resistance in the superconducting phase were observed at any in-plane field directions. The features were ascribed to the commensurability (CM) effect between the Josephson vortex lattice and the periodic nodal structure of the superconducting gap in the Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) phase. The CM effect was observed in a similar field region for various in-plane field directions, in spite of the anisotropic nature of the Fermi surface. The results clearly showed that the FFLO phase stability is insensitive to the in-plane field directions.

Thermodynamic investigation by calorimetric measurements of the layered organic superconductors, κ-(BEDT-TTF)2Cu[N(CN)2]Br and its partially deuterated compounds of κ-(d[2,2]-BEDT-TTF)2Cu[N(CN)2]Br and κ-(d[3,3]-BEDT-TTF)2Cu[N(CN)2]Br, performed in a wide temperature range is reported. The latter two compounds were located near the metal–insulator boundary in the dimer-Mott phase diagram. From the comparison of the temperature dependences of their heat capacities, we indicated that lattice heat capacities of the partially deuterated compounds were larger than that of the pristine compound below about 40 K. This feature probably related to the lattice softening was discussed also by the sound velocity measurement, in which the dip-like structures of the Δv/v were observed. We also discussed the variation of the electronic heat capacity under magnetic fields. From the heat capacity data at magnetic fields up to 6 T, we evaluated that the normal-state γ value of the partially deuterated compound, κ-(d[3,3]-BEDT-TTF)2Cu[N(CN)2]Br, was about 3.1 mJ K−2 mol−1. Under the magnetic fields higher than 3.0 T, we observed that the magnetic-field insulating state was induced due to the instability of the mid-gap electronic state peculiar for the two-dimensional dimer-Mott system. Even though the volume fraction was much reduced, the heat capacity of κ-(d[3,3]-BEDT-TTF)2Cu[N(CN)2]Br showed a small hump structure probably related to the strong coupling feature of the superconductivity near the boundary.

Professor Peter Day FRS was born on 20 August 1938 in Kent (UK) and attended Maidstone Grammar School [...]

Peter Day’s research group reported the first molecular superconductor containing paramagnetic metal ions in 1995, β″-(BEDT-TTF)4(H3O)Fe(C2O4)3·C6H5CN. Subsequent research has produced a multitude of BEDT-TTF-tris(oxalato)metallate salts with a variety of structures and properties, including 32 superconductors to date. We present here the synthesis, crystal structure, and conducting properties of the newest additions to the Day series including the first superconductor incorporating the diamagnetic tris(oxalato)aluminate anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, which has a superconducting Tc of ~2.5 K. β″-(BEDT-TTF)4(H3O)Co(C2O4)3·C6H5Br represents the first example of a β″ phase for the tris(oxalato)cobaltate anion, but this salt does not show superconductivity.

An organic anion, 2-bromoethanesulfonate (BrC2H4SO3−), provides one bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and two bis(ethylenedithio)tetraselenafulvalene (BETS) salts, the compositions of which are β’’-β’’-(BEDT-TTF)2BrC2H4SO3 (1), β’’-β’’-(BETS)2BrC2H4SO3 (2), and θ-(BETS)2BrC2H4SO3 (3), respectively. Compound 1 shows a metal–insulator transition at around 70 K. Compound 2 is isomorphous to 1, and 3 is polymorphic with 2. Compounds 2 and 3 show metallic behavior at least down to 4.2 K. The pressure dependence of the electrical resistivity of 1 is also reported.

Two novel salts containing the anion [Ni(mnt)2]− (mnt = maleonitriledithiolate) have been synthesized. The counter-ions, [Fe(II)(L1 or L2)2], are cationic complexes where L1 and L2 are methylated derivatives of 2,6-bis(pyazolyl)pyridine or pyrazine, which are similar to ligands found in a series of spin-crossover (SCO) complexes. Both salts are characterized by variable temperature single crystal X-ray diffraction and bulk magnetization measurements. Compound 1, [Fe(II)(L1)2][Ni(mnt)2]2 displays an incomplete and gradual SCO up to 300 K, followed by a more rapid increase in the high-spin fraction between 300 and 350 K. Compound 2, [Fe(II)(L2)2][Ni(mnt)2]2.MeNO2, shows a gradual, but more complete SCO response centered at 250 K. For compound 2, the SCO is confirmed by variable temperature Mössbauer spectroscopy. In both cases, the anionic moieties are isolated from each other and so no electrical conductivity is observed.

New bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)-, bis(ethylenediseleno)tetrathiafulvalene (BEST)- and bis(ethylenedithio)tetraselenafulvalene (BETS)-based organic charge-transfer (CT) salts—α-(BEDT-TTF)3(HOC2H4SO3)2 (1), β-(BEST)3(HOC2H4SO3)2·H2O (2) and α-(BETS)2(HOC2H4SO3)·H2O (3)—have been prepared. Salts 1 and 2 show semiconducting behaviour. Salt 3, which is almost isostructural to α-(BETS)2I3, shows metallic behaviour down to 70 K and then shows a broader metal–insulator transition than that of α-(BETS)2I3. The reason for the difference in behaviour is estimated by the comparison of the Madelung energies of the full set of patterns of possible donor’s charge-ordered and anion’s disordered states.

We investigate low-temperature electronic states of the series of organic conductors β^{′′}-[bis(ethylenedithio)tetrathiafulvalene]_{4}[(H_{3}O)M(C_{2}O_{4})_{3}]G, where M and G represent trivalent metal ions and guest organic molecules, respectively. Our structural analyses reveal that the replacement of M and G give rise to systematic change in the cell parameters, especially in the b-axis length, which has a positive correlation with the superconducting transition temperature T_{c}. Analysis of temperature and magnetic field dependences of the electrical resistance including the Shubnikov–de Haas oscillations elucidates that the variation of charge disproportionation, the effective mass, and the number of itinerant carriers can be systematically explained by the change of the b-axis length. The changes of the transfer integrals induced by stretching/compressing the b axis are confirmed by the band calculation. We discuss that electron correlations in quarter-filled electronic bands lead to charge disproportionation and the possibility of a novel pairing mechanism of superconductivity mediated by charge degrees of freedom.

Thermodynamic picture induced by π-d interaction in a molecular magnetic superconductor κ-(BETS)2FeX4 (X = Cl, Br), where BETS is bis(ethylenedithio)tetraselenafulvalene, studied by single crystal calorimetry is reviewed. Although the S = 5/2 spins of Fe3+ in the anion layers form a three-dimensional long-range ordering with nearly full entropy of Rln6, a broad hump structure appears in the temperature dependence of the magnetic heat capacity only when the magnetic field is applied parallel to the a axis, which is considered as the magnetic easy axis. The scaling of the temperature dependence of the magnetic heat capacity of the two salts is possible using the parameter of |Jdd|/kB and therefore the origin of the hump structure is related to the direct magnetic interaction, Jdd, that is dominant in the system. Quite unusual crossover from a three-dimensional ordering to a one-dimensional magnet occurs when magnetic fields are applied parallel to the a axis. A notable anisotropic field-direction dependence against the in-plane magnetic field was also observed in the transition temperature of the bulk superconductivity by the angle-resolved heat capacity measurements. We discuss the origin of this in-plane anisotropy in terms of the 3d electron spin configuration change induced by magnetic fields.

While an addition product was formed by the reaction of AZADO (2-azaadamantane N-oxyl) with TCNQF4 (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), the reaction of AZADO with thiourea provided an inclusion compound, in which AZADO molecules are incorporated in cylindrical channels formed by thiourea molecules.

Organic molecular conductors with a strongly correlated electron system, in which the itinerancy of electrons (or holes) and the electron correlation (U/W, U, the on-site Coulomb repulsion, W, the bandwidth) compete with each other, are promising candidates for achieving superconductivity and also for exploring remarkable physical properties induced by external stimuli such as pressure, light, voltage and current. Our synthetic approach to the construction of strongly correlated organic electron systems is based on chemical modifications to the donor molecule BDH-TTP [2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene] capable of producing metallic CT (charge-transfer) salts stable down to low temperatures (4.2–1.5 K). This aims at enhancing the electron correlation in the itinerant electron system by decreasing the bandwidth. Chemical modifications of BDH-TTP such as ring expansion of two outer dithiolane rings, replacement of one sulfur atom in an outer dithiolane ring with an oxygen atom and introduction of two methyl substituents into an outer ditiolane ring led to BDA-TTP [2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene], DHOT-TTP [2-(1,3-dithiolan-2-ylidene)-5-(1,3-oxathiolan-2-ylidene)-1,3,4,6-tetrathiapentalene] and DMDH-TTP [2-(4,5-dimethyl-1,3-dithiolan-2-ylidene)-5-(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene], respectively. In this review, the physical properties and the crystal and electronic structures of molecular conductors derived from these donor molecules will be described.

Three TCNQ derivatives carrying nitroxide radicals (3a–3c) were prepared and were found to form single-component charge-transfer (CT) complexes by self-assembly, in which outer nitroxide groups of a couple of different molecules work as donors and the inner TCNQ unit of another molecule as an acceptor. While the CT interactions found for the TEMPO (2,2,6,6-tetramethylpiperidin-1-oxy) derivative 3a and the PROXYL (2,2,5,5-tetramethylpirrolidin-1-oxy) derivative 3b are point-to-face fashion between the oxygen atom of each nitroxide group and the six-membered ring of inner TCNQ unit, the CT interactions found for the PO (2,2,5,5-tetramethyl-3-pyrrolin-1-oxy) derivative 3c are point-to-point contacts between the oxygen atoms of outer nitroxide groups and the carbon atoms of a couple of cyano groups.

A novel organic dianion, N,N'-Disulfo-1,4-benzoquinonediimine (1) has been prepared, which is a strong electron acceptor. The reduction potential of the PPh4 salt indicates that 1 is a stronger acceptor than DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone). The dianionic acceptor provided a BEDT-TTF salt, (BEDT-TTF)41·3H2O, the structures and physical properties of which are reported.

This article reviews and discusses the thermodynamic properties of dimer-Mott-type molecular superconductive compounds with (BEDT-TTF)2X composition, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene and X denotes counter-anions, respectively. We focus mainly on the features occurring in the κ-type structure in which the d-wave superconductive phase appears depending on the Coulomb repulsion U and the bandwidth W, which is tunable by external and chemical pressures. First, we report the high-pressure ac (alternating current) calorimetry technique and experimental system constructed to measure single-crystal samples of molecule-based compounds to derive low-temperature thermodynamic parameters. Using extremely small resistance chips as a heater and a thermometer allows four-terminal detection of an accurate temperature and its oscillation in the sample part with sufficient sensitivity. From the analyses of the temperature dependence of the ac heat capacity of κ-(BEDT-TTF)2Cu(NCS)2 under external pressures, we discuss the changes in the peak shape of the thermal anomaly at the superconductive transition temperature Tc at various external pressures p. The rather sharp peak in CpT−1 at Tc = 9.1 K with a strong coupling character at ambient pressure is gradually reduced to weaker coupling as the pressure increases to 0.45 GPa concomitant with suppression of the transition temperature. This feature is compared with the systematic argument of the chemical–pressure effect on the basis of thermal anomalies around the superconductive transition of κ-(BEDT-TTF)2X compounds and other previously studied typical dimer-Mott 2:1 compounds. Finally, the discussion is extended to the chemical pressure effect on the normal state electronic heat capacity coefficient γ obtained by applying magnetic fields higher than Hc2 and the residual γ*, which remains in the superconductive state due to the induced electron density of states around the node structure. From the overall arguments with respect to both chemical and external pressures, we suggest that a crossover of the electronic state inside the superconductive phase occurs and the coupling strength of electron pairs varies from the electron correlation region near the metal-insulator boundary to the band picture region.

Three kinds of molecular complexes based on tetrathiafulvalene (TTF) and dialkylviologens were prepared and their crystal structures elucidated. While TTF-dimethylviologen complex forms a mixed stack arrangement of donors and acceptors in its crystal structure, TTF donors aggregate with long alkyl groups by CH/p and/or van der Waals interactions in a couple of TTF-heptylviologen complexes.

Three N-salicylideneamine derivatives bearing TEMPO (2,2,6,6-tetra- methyl-1-piperidinyloxy) substituents were prepared in order to study their structure and property relationships and to investigate the possibilities of the existence of heat and/or light responsive magnetic properties. Curie-Weiss behavior with weak ferromagnetic intermolecular spin-spin interactions was observed in one of the radicals, while antiferromagnetic interactions were predominant for the other radicals and the structure-property relationships were investigated for the radical compounds from their crystal structures obtained by X-ray analyses. Preliminary results of the examination of their responses towards light and heat are also described.

Regarding the fabrication of solar selective absorbers, the ability to create microstructures on top of metal surfaces is a promising technology. Typically, these materials are able to possess spectrally-selective absorption properties for high-temperature usage. Solar-selective absorbers that function at temperatures up to 700 °C and possess shallow honeycomb cylindrical microcavities coated with a metal-dielectric multi-layer have been investigated. Honeycomb array cylindrical microcavities were fabricated on W substrate with interference lithography and multi-layers consisting of Pt nano-film sandwiched by Al2O3 layers were created for a uniform coating via atomic layer deposition. The absorbance spectrum of fabricated samples reveals results consistent with a simulation based on a rigorous coupled-wave analysis method. A solar absorbance value of 0.92 and a hemispherical total emittance value of 0.18 at 700 °C was determined from the fabricated solar-selective absorber. Additionally, thermal stability of up to 700 °C was confirmed in vacuum.

Radical-cation salts of formula β?-(BEDT-TTF)4[(H3O)Fe(C2O4)3]·guest have produced a large number of superconductors and provided a route to introduce magnetism and chirality into the same multifunctional material. A relationship has been found in these salts between the length of the b axis and the superconducting Tc. Increasing the b axis length by introducing larger guest molecules, such as benzonitrile and nitrobenzene, gives the highest superconducting Tcs in this family of salts. Smaller guests such as pyridine show no superconducting transition, whilst asymmetrical guests which are larger than nitrobenzene have given a different bilayered structure. Other potential guest molecules have been limited by their ability to be used as the solvent in which the crystals are grown via electrocrystallisation. This paper reports a method which introduces guest molecules into the crystal which are a solid or liquid additive within the crystal-growing solvent 1,2,4-trichlorobenzene:ethanol. We present the crystal structures of five new BEDT-TTF radical-cation salts with tris(oxalato)ferrate anions using guest molecules toluene, phenol, benzaldehyde, 4-bromobenzaldehyde, and kojic acid. [ABSTRACT FROM AUTHOR]