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The organic system, $\kappa$-[(BEDT-TTF)$_{1-x}$(BEDT-STF)$_x$]$_2$Cu$_2$(CN)$_3$, showing the Mott transition between a nonmagnetic Mott insulating (NMI) state and a Fermi liquid (FL), is systematically studied by calorimetric measurements. An increase of the electronic heat capacity at the transition from the NMI state to the FL state which keeps the triangular dimer lattice demonstrates that the charge sector lost in the Mott insulating state is recovered in the FL state. We observed that the remaining low-energy spin excitations in the Mott insulating state show unique temperature dependence, and that the NMI state has a larger lattice entropy originating from the frustrated lattice, which leads to the Pomeranchuk-like effect on the electron localization. Near the Mott boundary, an unexpected enhancement and magnetic-field dependence of heat capacity are observed. This anomalous heat capacity is different from the behavior in the typical first-order Mott transition and shows similarities with quantum critical behavior. To reconcile our results with previously reported scenarios about a spin gap and the first-order Mott transition, further studies are desired., Comment: 9 pages, 4 figures

We report the water adsorption/desorption behavior and dynamic magnetic properties of the Pt-Cl chain complex [{[Pt(en)

The construction of a thermal conductivity measurement system designed for tiny molecules-based compounds is reported. We introduce complementary usage of chip-type RuO2 thermometers and E-type thermocouples in the sample part by using thin (ϕ 13μm) constantan and chromel wires. Two pairs of the constantan and chromel wires are used as lead wires for the four-terminal measurement of the resistance of RuO2 thermometers in the low-temperature region below about 20 K. Also, in the higher temperature region above 10 K up to room temperature with the overlapping range of 10-20 K, they are used as thermocouples for detecting temperature differences from that of the heat sink. We also compare a kind of resolution parameter of several sensors as a function of temperature to discuss the rational reason to select suitable sensors depending on the temperature region. Using the constructed apparatus, we report temperature dependences of the thermal conductivity of deuterated κ-(d8:BEDT-TTF)2Cu[N(CN)2]Br in a wide temperature range between 2 and 250 K. The result provides convincing evidence for the validity of the newly developed system for the thermal measurements of molecular crystals.

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.

Single crystal X-ray diffraction, magnetic and 57Fe Mossbauer spectroscopic studies of a new iron(II)-based spin transition complex – [Fe(3-bpp)2](CF3COO)2 (bpp = 2,6-bis(pyrazol-3-yl)pyridine) are reported. The complex exhibits an incomplete thermal high spin (HS) low spin (LS) transition at ∼226 K which is not associated with any crystallographic transition. Only one of the two crystallographic iron(II) sites undergoes the spin transition, while the other HS site remains invariant of temperature down to 10 K. The origin of the incomplete spin transition is understood by analysing the nature of crystal packing below and above the transition temperature with special attention to the degree of distortion. The present study shows the role of the degree of distortion associated with the cations in the [Fe(3-bpp)2]2+ spin transition complexes.

We report the first example of a chiral BDH-TTP radical-cation salt. Chirality is induced in the structure via the use of a chiral spiroboronate anion where three stereocentres are present, one on each chiral ligand and one on the boron centre. Despite starting from a labile racemic mixture of BS and BR enantiomers, only one enantiomer is present in the crystal lattice. The anions pack in a novel double anion layer which is the thickest anion layer found in a BDH-TTP salt. This material is chiral and shows metallic behaviour down to at least 4.2 K.

We present the synthesis, crystal structures and conducting properties of six new BEDT-TTF radical-cation salts with the tris(oxalato)gallate or -iridate anion. The use of halobenzenes gives 4 : 1 β′′ metallic or superconducting salts with tris(oxalato)gallate - fluorobenzene (PhF) or chlorobenzene (PhCl) as a guest molecule gives a metal, whilst the larger bromobenzene (PhBr) or iodobenzene (PhI) gives a superconductor. A 4 : 1 pseudo-κ semiconducting salt is obtained with benzonitrile as the guest molecule for tris(oxalato)iridate, and a novel 5 : 1 metal-insulator phase with tris(oxalato)iridate is also reported.

A new bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)-based salt with an organic magnetic anion, PO-CONHCH(cyclopropyl)SO3−, has been prepared (PO = 2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl free radi...

Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K6 [Rh4 Zn4 O(l-cys)12 ] (K6 [1]; l-H2 cys=l-cysteine) in a water/ethanol solution containing Ln(OAc)3 (Ln3+ =lanthanide ion) results in the exchange of K+ by Ln3+ with retention of the single crystallinity, producing Ln2 [1] (2Ln ) and Ln0.33 [Ln4 (OH)4 (OAc)3 (H2 O)7 ][1] (3Ln ) for early and late lanthanides, respectively. While the Ln3+ ions in 2Ln exist as disordered aqua species, those in 3Ln form ordered hydroxide-bridged cubane clusters that connect [1]6- anions in a 3D metal-organic framework through coordination bonds with carboxylate groups. This study shows the utility of an anionic metallosupramolecular framework with carboxylate groups for the creation of a series of metal cubanes that have great potential for various applications, such as magnetic materials and heterogeneous catalysts.

The chiral and racemic salts β′′-(BEDT-TTF)2(S- and rac-PROXYL-CONHCH2SO3) (S-2 and rac-2) are almost isomorphous apart from a deviation in the C–H bond direction at the chiral centre. Both salts are metallic at room temperature, with similar broad metal-insulator transitions. Band structure calculations of the chiral and racemic salts indicate that both electronic structures are quite similar. However, at 30 K, S-2 has a resistivity that is nearly three orders of magnitude higher than that of rac-2. The results suggest a significant effect of the broken inversion symmetry, due to the positional change of only one atom.

Materials exhibiting both chirality and conductivity do not exist in nature and very few examples have been synthesised. We report here the synthesis of a chiral molecular metal which remains metallic down to at least 4.2 K. This material also exhibits room-temperature switching capabilities with a transition upon cooling below 10 °C.

We report the first examples of radical-cation salts of BEDT-TTF with spiroborate anions [B(mandelate)

We report here a structurally perfect kagomé lattice {[Cu_3(bpy)_6](SiF_6)_3(melamine)_8}_n (1), where bpy is 4,4′-bipyridine and [SiF_6]^2− is a hexafluorosilicate anion. In comparison to general 1D linear, 2D layered and 3D cubic metal–organic frameworks, by using Cu^2+ nodes and bpy ligands, a perfect kagomé lattice was synthesized by introducing C_3 symmetrical melamine molecules. Magnetic susceptibility and low-temperature heat capacity measurements indicated weak antiferromagnetic interactions between the spins and no long-range magnetic ordering to 0.7 K. Using C_3 symmetrical melamine molecules can be considered as a challenging synthetic strategy to afford new topological materials.

We report the first examples of radical-cation salts of BEDT-TTF with spiroborate anions [B(mandelate)2]− and [B(2-chloromandelate)2]−, synthesized from either enantiopure or racemic bidentate mandelate or chloromandelate ligands. In the salts prepared using enantiopure ligands only one of two diastereoisomers of the spiroborate anion is incorporated, with the boron centre having the same stereochemistry as the enantiopure ligand. For the racemic salts one racemic pair of spiroborate anions containing an R and an S mandelate ligand is incorporated. In certain solvents helical crystals were obtained when using spiroborate anions with enantiopure ligands. Electrical and magnetic properties, and band structure calculations are reported.

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 $\alpha$-(BETS)$_2$I$_3$. The surface metallic state that emerges at low temperatures exhibits characteristic transport properties of a gapless Dirac semimetal, evidencing the presence of a topological surface state in this compound. 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., Comment: 36 pages including 10 figures

The ion-conducting behaviour of alkali metal ions in ionic solids (M6[1]·nH2O) resembles that in aqueous solutions; the solid-state conductivities increase in the order of M = Li+ < Na+ < K+., The design and creation of ionic crystals that show high mobility of ionic species in the solid state has long been a research topic of considerable attention not only due to the practical applications of these materials but also due to the correlation of such ionic species with ion-transport biological systems. In this work, we report the mobility of alkali metal ions (M = Li+, Na+, K+) in the ionic crystals M6[Rh4Zn4O (l-cysteinate)12]·nH2O (M6[1]·nH2O). In M6[1]·nH2O, alkali metal ions are distributed in a disordered manner, together with a number of water molecules, within a rigid hydrogen-bonded framework of anionic clusters of [1]6–. The alternating current conductivities of M6[1]·nH2O in the solid state increase in the order of Li6[1]·nH2O < Na6[1]·nH2O < K6[1]·nH2O, which is opposite to the order of the naked ionic radii. The conductivities reach the superionic level of σ = 1.3 × 10–2 S cm–1 at 300 K for a single crystal of K6[1]·nH2O. These results reflect the high mobility of hydrated alkali metal ions in the crystal lattice of M6[1]·nH2O, which is supported by solid-state NMR spectroscopy, together with ion diffusion experiments in the solid state. The high mobility leads to quick exchange of K+ ions in K6[1]·nH2O with Li+ and Na+ ions with retention of single crystallinity.

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.

Quantum spin liquids (QSLs), in which spins are highly entangled, have been considered a groundwork for generating exotic superconductivity. Despite numerous efforts, superconductivity emerging from QSLs has been unrealized in actual materials due to the difficulties in stabilizing QSL states with metallic conductivity. Recently, an organic compound, $\ensuremath{\kappa}\text{\ensuremath{-}}{(\mathrm{BEDT}\text{\ensuremath{-}}\mathrm{TTF})}_{4}{\mathrm{Hg}}_{2.89}{\mathrm{Br}}_{8}$, with a nearly regular triangular lattice of molecular dimers was recognized as a candidate for doped QSLs. In this study, we report an unusual superconducting phase of $\ensuremath{\kappa}\text{\ensuremath{-}}{(\mathrm{BEDT}\text{\ensuremath{-}}\mathrm{TTF})}_{4}{\mathrm{Hg}}_{2.89}{\mathrm{Br}}_{8}$: unexpectedly large ratios of the upper critical field to the critical temperature ${H}_{\mathrm{c}2}/{T}_{\mathrm{c}}$ in fields not only parallel but also perpendicular to the two-dimensional conducting layers and a very wide region of fluctuating superconductivity above ${T}_{\mathrm{c}}$. Our results reveal that these peculiarities arise from strong electron correlations and possible quantum criticality unique to the doped QSL state, leading to a heavy mass of itinerant carriers and a large superconducting energy gap.

In this work, the thermodynamic properties of the organic superconductor $\ensuremath{\lambda}\text{\ensuremath{-}}{(\mathrm{BETS})}_{2}{\mathrm{GaCl}}_{4}$ are investigated to study a high-field superconducting state known as the putative Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) phase. We observed a small thermodynamic anomaly in the field ${H}_{\mathrm{FFLO}}\phantom{\rule{4pt}{0ex}}\ensuremath{\sim}10$ T, which corresponds to the Pauli limiting field ${H}_{\mathrm{P}}$. This anomaly probably originates from a transition from a uniform superconducting state to the FFLO state. ${H}_{\mathrm{FFLO}}$ does not show a strong-field angular dependence due to a quasi-isotropic paramagnetic effect in $\ensuremath{\lambda}\text{\ensuremath{-}}{(\mathrm{BETS})}_{2}{\mathrm{GaCl}}_{4}$. The thermodynamic anomaly at ${H}_{\mathrm{FFLO}}$ is smeared out. and the low-temperature upper critical field ${H}_{\mathrm{c}2}$ changes significantly if fields are not parallel to the conducting plane, even for a deviation of $\ensuremath{\sim}0.{5}^{\ensuremath{\circ}}$. This behavior indicates that the high-field state is very unstable, as it is influenced by the strongly anisotropic orbital effect. Our results are consistent with the theoretical predictions on the FFLO state and show that the high-field superconductivity is probably an FFLO state in $\ensuremath{\lambda}\text{\ensuremath{-}}{(\mathrm{BETS})}_{2}{\mathrm{GaCl}}_{4}$ from a thermodynamic point of view.

We report the first example of a chiral BDH-TTP radical-cation salt. Chirality is induced in the structure via the use of a chiral spiroboronate anion where three stereocentres are present, one on each chiral ligand and one on the boron centre. Despite starting from a labile racemic mixture of BS and BR enantiomers, only one enantiomer is present in the crystal lattice. The anions pack in a novel double anion layer which is the thickest anion layer found in a BDH-TTP salt. This material is chiral and shows metallic behaviour down to at least 4.2 K.

We investigate low-temperature electronic properties of the nondimeric organic superconductor $\beta^{\prime\prime}$-(BEDT-TTF)$_4$[(H$_3$O)Ga(C$_2$O$_4$)$_3$]PhNO$_2$. By examining ultrasonic properties, charge disproportionation (CD) without magnetic field dependence is detected below $T_{\rm CD}$$\sim$8~K just above the superconducting critical temperature $T_{\rm c}$$\sim$6~K. From quantum oscillations in high fields, we find variation in the Fermi surface and mass enhancement induced by the CD. Heat capacity studies elucidate that the superconducting gap function is fully gapped in the Fermi surface, but anisotropic with fourfold symmetry. We point out that the pairing mechanism of the superconductivity is possibly dominated by charge fluctuations., Comment: 6 figures

We newly constructed a thermal conductivity measurement system for single crystals of molecular compounds. This system enables us to measure the thermal conductivity of samples with the length of less than 1.0 mm. In order to evaluate the capability of detection of phase transitions occurred in molecule-based materials, we performed the thermal conductivity measurement of single crystals of organic conductors α-(BEDT-TTF)2I3 and κ-(BEDT-TTF)2Cu[N(CN)2]Br, where BEDT-TTF denotes bis(ethylenedithio)tetrathiafulvalene. From the temperature dependence of the thermal conductivity of α-(BEDT-TTF)2I3, we succeeded in observing the metal–insulator transition as a sudden drop of κ(T) at 135 K. In the temperature dependence of thermal conductivity of κ-(BEDT-TTF)2Cu[N(CN)2]Br, we could observe the increment of κ(T) at the metal-superconducting transition (Tc = 11.4 K). These results show that the newly developed system has high performance enough to detect various kinds of phase transitions in small crystals of molecular compounds.

A new Ni(dmit)2-based organic magnetic charge-transfer (CT) salt, (m-PO-CONH-N-methylpyridinium)[Ni(dmit)2]·CH3CN, where PO = 2,2,5,5-Tetramethyl-3-pyrrolin-1-oxyl free radical and dmit = 2-Thioxo-1,3-dithiole-4,5-dithiolate, was obtained, the crystal structure and magnetic properties of which are reported. Magnetic susceptibility of the CT salt obeys a combination of 1D ferromagnetic (1DF) Heisenberg (J1DF = +0.26 K) and Singlet-Triplet (ST) models (JST = -51.2 K) with mean field (MF) approximation (JMF = -6.7 K), suggesting that spins on the PO radicals form 1D ferromagnetic chains and spins on the Ni(dmit)2 monoanions forms spin dimers at low temperature, the latter of which was also confirmed by band calculations.