BEDT-TTF radical-cation salts with tris(oxalato)chromate and guest additives.

The family of radical-cation salts ß''-(BEDT-TTF)4[(A)M3+(C2O4)3]·guest (M = Fe, Cr, Ga, Al, Co, Mn, Rh, Ru; A = K+, H3O+, NH4 +) has produced superconductors, metals, semiconductors, and metal-insulators through introduction of different guest molecules into the structure. We present three new additions to the family ß''-(BEDT-TTF)4[(A)Cr(C2O4)3]·guest with the guest molecules toluene, phenol, or salicylaldehyde. These new guests are liquid or solid additives within the electrocrystallisation medium. All three salts show metallic behaviour from room temperature down to <10 K and do not show a superconducting transition.

J_{eff}=1/2 Hyperoctagon Lattice in Cobalt Oxalate Metal-Organic Framework.

We report the magnetic properties of a cobalt oxalate metal-organic framework featuring the hyperoctagon lattice. Our thermodynamic measurements reveal the J_{eff}=1/2 state of the high-spin Co^{2+} (3d^{7}) ion and the two successive magnetic transitions at zero field with two-stage entropy release. ^{13}C-NMR measurements reveal the absence of an internal magnetic field in the intermediate temperature phase. Multiple field-induced phases are observed before full saturation at around 40 T. We argue the unique cobalt oxalate network gives rise to the Kitaev interaction and/or a bond frustration effect, providing an unconventional platform for frustrated magnetism on the hyperoctagon lattice.

Quantum Liquid States of Spin Solitons in a Ferroelectric Spin-Peierls State.

In this study, we performed high-magnetic-field magnetization, dielectric, and ultrasound measurements on an organic salt showing a ferroelectric spin-Peierls (FSP) state, which is in close proximity to a quantum critical point. In contrast to the sparsely distributed gaslike spin solitons typically observed in conventional spin-Peierls (SP) states, the FSP state exhibits dense liquidlike spin solitons resulting from strong quantum fluctuations, even at low fields. Nevertheless, akin to conventional SP systems, a magnetic-field-induced transition is observed in the FSP state. In conventional high-field SP states, an emergent wave vector results in the formation of a spin-soliton lattice. However, in the present high-field FSP state, the strong quantum fluctuations preclude the formation of such a soliton lattice, causing the dense solitons to remain in a quantum-mechanically melted state. This observation implies the realization of a quantum liquid-liquid transition of topological particles carrying spin and charge in a ferroelectric insulator.

Insights into Thermal Transport through Molecular π-Stacking.

π-Stacking, which is a ubiquitous structural motif in assemblies of aromatic compounds, is well-known to provide a transport pathway for charge carriers and excitons, while its contribution to thermal transport is still unclear. Herein, based on detailed experimental observations of the thermal diffusivity, thermal conductivity, and specific heat of a single-crystalline triphenylene featuring a one-dimensionally π-stacked structure, we describe the nature of thermal transport through the π-stacked columns. We reveal that acoustic phonons are responsible for thermal transport through the π-stacked columns, which exhibit crystal-like behavior. Importantly, the thermal energy stored as intramolecular vibrations can also be transported by coupling to the acoustic phonons. In contrast, in the direction perpendicular to the π-stacked columns, an amorphous-like thermal transport behavior dominates. The present finding offers deep insight into nanoscale thermal transport in organic materials, where the constituent molecules exist as discrete entities linked together by weak intermolecular interactions.

Correlation-driven organic 3D topological insulator with relativistic fermions.

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.

Emergent anisotropy in the Fulde-Ferrell-Larkin-Ovchinnikov state.

Exotic superconductivity is formed by unconventional electron pairing and exhibits various unique properties that cannot be explained by the basic theory. The Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state is known as an exotic superconducting state in that the electron pairs have a finite center-of-mass momentum leading to a spatially modulated pattern of superconductivity. The spatial modulation endows the FFLO state with emergent anisotropy. However, the anisotropy has never been experimentally verified despite numerous efforts over the years. Here, we report detection of anisotropic acoustic responses depending on the sound propagation direction appearing above the Pauli limit. This anisotropy reveals that the two-dimensional FFLO state has a center-of-mass momentum parallel to the nesting vector on the Fermi surface. The present findings will facilitate our understanding of not only superconductivity in solids but also exotic pairings of various particles.

High-resolution calorimetry in pulsed magnetic fields.

We have developed a new calorimeter for measuring the thermodynamic properties in pulsed magnetic fields. Instrumental design is described along with the instrument construction details, including the sensitivity of a RuO2 thermometer. Operation of the calorimeter is demonstrated by measuring the heat capacity of three samples: pure germanium, CeCu2Ge2, and κ-(BEDT-TTF)2Cu[N(CN)2]Br, in pulsed fields up to 43.5 T. Obtaining field stability is key in measuring high-resolution heat capacity under pulsed fields. We also examine the performance of the calorimeter by employing two measurement techniques: the quasi-adiabatic and dual-slope techniques. We demonstrate that the calorimeter developed in this study is capable of performing high-resolution calorimetry in pulsed magnetic fields, which opens the door to new opportunities for high-field thermodynamic studies.

2D Molecular Superconductor to Insulator Transition in the ß''-(BEDT-TTF)2[(H2O)(NH4)2M(C2O4)3]·18-crown-6 Series (M = Rh, Cr, Ru, Ir).

The series of salts ß''-(BEDT-TTF)2[(H2O)(NH4)2M(C2O4)3]·18-crown-6 show ambient-pressure superconductivity when M = Cr, Rh. Evidence indicates that the previously reported Cr and Rh salts show a bulk Berezinski-Kosterlitz-Thouless superconducting transition. The isostructural ruthenium and iridium salts are reported here. The Ir salt represents the first radical-cation salt to contain a 5d tris(oxalato)metalate anion. The Ru and Ir salts do not show superconductivity but instead undergo a broad chemically induced metal to insulator transition at 155 K for ruthenium and at 100 K for iridium. The c axes of the Ru and Ir salts are much shorter than those of the Rh and Cr salts. Thus, the more stable metallic state of the Cr and Rh salts is associated with the more strongly 2D electronic systems. The different low-temperature behavior of the Ru and Ir salts, which exhibit a smaller interlayer spacing, could originate from a structural change in the anionic layer which thus can be easily transmitted to the donor layers and generate a localized state. However, another possibility is that it originates from Berezinski-Kosterlitz-Thouless effects.

Bulk Kosterlitz-Thouless Type Molecular Superconductor ß″-(BEDT-TTF)2[(H2O)(NH4)2Cr(C2O4)3]·18-crown-6.

A new molecular superconductor, ß″-(BEDT-TTF)2[(H2O)(NH4)2Cr(C2O4)3]·18-crown-6, has been synthesized from the organic donor molecule BEDT-TTF with the anion Cr(C2O4)33-. The crystal structure consists of conducting organic layers of BEDT-TTF molecules which adopt the ß″ packing motif (layer A), layers of NH4+ and Λ-Cr(C2O4)33- (layer B), layers of (H2O)(NH4)18-crown-6 (layer C), and layers of NH4+ and Δ-Cr(C2O4)33- (layer D) which produce a superstructure with a repeating pattern of ABCDABCDA. As a result of this packing arrangement, this is the 2D superconductor with the widest gap between conducting layers where only a single donor packing motif is present (ß″). Superconducting critical temperatures at ambient pressure observed by electrical transport and magnetic measurements are 4.0-4.9 and 2.5 K, respectively. The strong 2D nature of this system, the broad transition to Tzero at 1.8K, and the transition of α of V ∝ Iα from 1 to 3 on I-V curves strongly suggest that the superconducting transition is very close to a Kosterlitz-Thouless transition. The magnetic field dependence of the superconducting critical temperature parallel to the conducting plane gives an upper critical field µ0Hc2∥ > 8 T, which is over the calculated Pauli-Clogston limit for this material.

Molecular conductors from bis(ethylenedithio)tetrathiafulvalene with tris(oxalato)rhodate.

This article reports a family of new radical-cation salts of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with tris(oxalato)rhodate: three salts with the formula ß''-(BEDT-TTF)4[(cation)Rh(C2O4)3]·solvent (solvent = fluorobenzene, chlorobenzene, or bromobenzene) and one with the formula pseudo-κ-(BEDT-TTF)4[(NH4)Rh(C2O4)3]·benzonitrile. We report here the syntheses, crystal structures, electrical properties and Raman spectroscopy of these new molecular conductors. The bromobenzene salt shows a decrease in resistivity below 2.5 K indicative of a superconducting transition and a Shubnikov-de Haas oscillation with a frequency of 232 T and effective mass m* of 1.27me.

Ambient-pressure molecular superconductor with a superlattice containing layers of tris(oxalato)rhodate enantiomers and 18-crown-6.

We report a novel multilayered organic-inorganic hybrid material, ß″-(BEDT-TTF)2[(H2O)(NH4)2Rh(C2O4)3]·18-crown-6. This is the first molecular superconductor to have a superlattice with layers of both BEDT-TTF and 18-crown-6 and also the first with the anion tris(oxalato)rhodate. This is the 2D superconductor with the widest gap between conducting layers, where only a single donor packing motif is observed (ß″). The strong 2D nature of this system strongly suggests that the superconducting transition is a Kosterlitz-Thouless transition. A superconducting Tc of 2.7 K at ambient pressure was found by transport measurements and 2.5 K by magnetic susceptibility measurements.