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.

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.

Enantiopure and racemic radical-cation salts of B(mandelate)2- and B(2-chloromandelate)2- anions with BEDT-TTF.

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.

Exceptionally high temperature spin crossover in amide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complex revealed by variable temperature Raman spectroscopy and single crystal X-ray diffraction.

The synthesis of a novel amide-functionalised 2,6-bis(pyrazol-1-yl)pyridine-4-carboxamide ligand (bppCONH2) is described. The complex salts [Fe(bppCONH2)2](BF4)2 and [Fe(bppCONH2)2](ClO4)2 were synthesised and characterised by SQUID magnetometry, differential scanning calorimetry, variable temperature Raman spectroscopy and single crystal X-ray diffraction. DSC measurements of [Fe(bppCONH2)2](BF4)2 indicate a spin-crossover (SCO) transition with T↑ at 481 K and T↓ at 461 K, showing a 20 K hysteresis. DSC for the perchlorate salt shows an SCO transition with T↑ at 459 K and T↓ at 445 K with a 14 K hysteresis. For the BF4- salt analysis of low and high-spin state crystal structures at 101, 290 and 500 K, suggest stabilisation of the low spin state due to the formation of 1D hydrogen-bonded cationic chains. Variable temperature Raman studies of the BF4 salt support the presence of a high temperature SCO. It is speculated that the presence of hysteresis may be attributed to differences in the inter-molecular hydrogen bonding in the low spin and high spin states.

Chiral metal down to 4.2 K - a BDH-TTP radical-cation salt with spiroboronate anion B(2-chloromandelate)2.

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.

Electric dipole induced bulk ferromagnetism in dimer Mott molecular compounds.

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.

Large-Amplitude Thermal Vibration-Coupled Valence Tautomeric Transition Observed in a Conductive One-Dimensional Rhodium-Dioxolene Complex.

The exploration of dynamic molecular crystals is a fascinating theme for materials scientists owing to their fundamental science and potential application to molecular devices. Herein, a one-dimensional (1D) rhodium-dioxolene complex is reported that exhibits drastic changes in properties with the phase transition. X-ray photoelectron spectroscopy (XPS) revealed that the room-temperature (RT) phase is in a mixed-valence state, and therefore, the drastic changes originate from the mixed-valence state appearing in the RT phase. Another notable feature is that the mean square displacements of the rhodium atoms along the 1D chain dramatically increased in the RT phase, indicating a large-amplitude vibration of the Rh-Rh bonds. From these results, a possible mechanism for the appearance of the mixed-valence state in the RT phase was proposed based on the thermal electron transfer from the 1D d-band to the semiquinonato π* orbital coupled with the large-amplitude vibration of the Rh-Rh bonds.

Chiral molecular conductor with an insulator-metal transition close to room temperature.

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.

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.

Above room temperature spin crossover in thioamide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complexes.

This work describes the synthesis of two novel functionalised 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands, namely 2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNH2) and N-methyl-2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNHMe). The corresponding solvated or non-solvated Fe(ii) salts, [Fe(bppCSNH2)2]X2 and [Fe(bppCSNHMe)2]X2 (X = BF4- or ClO4-) were synthesised and their properties measured by SQUID magnetometry, Evans NMR, differential scanning calorimetry and single crystal X-ray diffraction. In the solid state [Fe(bppCSNH2)2]2+ salts persist in the low spin state below 350 K. The structure of [Fe(bppCSNH2)2](BF4)2·2MeNO2 shows a network of intermolecular interactions responsible for the low spin state stabilisation, relative to the prototypical [Fe(bpp)2]2+ spin crossover (SCO) salts. By contrast the complexes of bppCSNHMe both display abrupt SCO above 300 K. [Fe(bppCSNHMe)2](BF4)2·MeNO2 requires solvent loss before SCO can be observed centred at 332 K. The non-solvated [Fe(bppCSNHMe)2](ClO4)2 shows SCO centred at 325 K. Analysis of solvated and non-solvated crystal structures suggests that cooperativity is facilitated by thioamide-group interactions with neighbouring pyrazolyl and pyridyl moieties.

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.

Enantiopure and racemic radical-cation salts of bis(2'-hydroxylpropylthio)(ethylenedithio)TTF with polyiodide anions.

The chiral TTF-based donor molecule bis(2'-hydroxylpropylthio)(ethylenedithio)tetrathiafulvalene (BHPT-EDT-TTF) has produced enantiopure R,R and S,S radical-cation salts with polyiodide anions I3- and I82-. Enantiomorphic 6 : 6 donor : I3 phases grown from either the R,R or S,S donor are semiconducting with similar activation energies of 0.24-0.30 eV and 0.22-0.23 eV, respectively, and contain three unique face-to-face donor pairs whose relative orientation is determined by side chain conformations and hydrogen bonding. Racemic material under the same conditions gave an insulating centrosymmetric phase with R,R and S,S donor cations in a face-to-face pair partnered with an octaiodide dianion, and with a ca. 3 : 1 disorder between the enantiomers. Enantiopure BHPT-EDT-TTF yielded two further insulating crystalline phases of composition 2 : 2 with triiodide and 2 : 1 with octaiodide.

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.

Coordination Chemistry of 2,2'-Bipyridyl- and 2,2':6',2″-Terpyridyl-Substituted BEDT-TTFs: Formation of a Supramolecular Capsule Motif by the Iron(II) Tris Complex of 2,2'-Bipyridine-4-thiomethyl-BEDT-TTF.

Molecules of tris(2,2'-bipyridine-4-thiomethyl-BEDT-TTF)iron(II) (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) assemble in pairs to form a novel supramolecular capsular structure in the solid state. Three BEDT-TTF residues from one complex lie in the three grooves between coordinated bipyridines of the other complex, and vice versa, to form a capsule with 3-fold rotational symmetry and an internal volume of ca. 160 Å(3). Further aspects of the coordination chemistry of this ligand, its 6-substituted isomer, and the 2,2':6'2″-terpyridyl-4'-thiomethyl-BEDT-TTF analogue are described.

Enantiopure and racemic radical-cation salts of B(malate)2(-) anions with BEDT-TTF.

We have synthesized the first examples of radical-cation salts of BEDT-TTF with chiral borate anions, [B(malate)2](-), prepared from either enantiopure or racemic bidentate malate ligands. In the former case only one of two diastereoisomers of the borate anion is incorporated, while for the hydrated racemic salt one racemic pair of borate anions containing a R and a S malate ligand is incorporated. Their conducting and magnetic properties are reported. The tight-binding band calculation indicates that the chiral salt has an effective half-filled flat band, which is likely to be caused by the chiral structural feature.

Radical-cation salts of BEDT-TTF with lithium tris(oxalato)metallate(III).

The first radical-cation salts in the extensive family (BEDT-TTF)x[(A)M(C2O4)3]·Guest containing lithium as the counter cation have been synthesized and characterised.

A series of two oxidation reactions of ortho-alkenylbenzamide with hypervalent iodine(III): a concise entry into (3R,4R)-4-hydroxymellein and (3R,4R)-4-hydroxy-6-methoxymellein.

A sequence of oxidation reactions of alkenamides with hypervalent iodine is described. Oxidation of ortho-alkenylbenzamide substrates selectively gave isochroman-1-imine products. The products underwent further oxidation in the presence of a Pd salt catalyst leading to regioselective C-H acetoxylation at the 8-position. A series of oxidations was applied to the crucial steps of asymmetric synthesis of 4-hydroxymellein derivatives.

Structures and properties of a BEDT-TTF-based organic charge transfer salt and the zwitterion of ferrocenesulfonate.

The structure and properties of a new semiconducting BEDT-TTF-based charge-transfer salt containing the ferrocenesulfonate (Fc-SO3(-)) anion, α-(BEDT-TTF)2Fc-SO3·2.5H2O, are described. The structure and magnetic properties of a zwitterion of ferrocenesulfonate, Fc(+)-SO3(-), are also reported.

Structures of the reaction products of the AZADO radical with TCNQF4 or thiourea.

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.