Charge ordering and carrier generation by air oxidation of a nickel complex with selenium-containing extended-tetrathiafulvalenedithiolate ligands.

The structures and electrical properties of ((n)Bu(4)N)[Ni(dmstfdt)(2)] (1), ((n)Bu(4)N)(2)[Ni(dmstfdt)(2)] (2), and ((n)Bu(4)N)(3)[Ni(dmstfdt)(2)](2) (3), where dmstfdt = extended-tetrathiafulvalenedithiolate ligand, were examined. The fresh crystal of 1 was found to be a Mott insulator, but the crystal gradually became highly conducting because of air oxidation. Compound 3 exhibited a semiconducting charge-ordering state.

Systemic Lupus Erythematosus Complicated with Listeria Monocytogenes Infection in a Pregnant Woman.

A 41-year-old woman with systemic lupus erythematosus (SLE) was admitted to our hospital due to a fever at 35 weeks of pregnancy. Laboratory testing revealed a low platelet count and elevated liver enzymes. Emergency Caesarean section was performed due to the risk of SLE exacerbation or hemolytic anemia, elevated liver enzyme, and low platelet count syndrome. Based on the blood culture results, the patient was diagnosed with Listeria monocytogenes bacteremia. She was treated with ampicillin and eventually recovered, and the neonate did not have any complications. Pregnant women with SLE are at risk of complications. Listeriosis should be monitored for and, if found, managed appropriately.

Conducting dimerized cobalt complexes with tetrathiafulvalene dithiolate ligands.

To obtain novel single-component molecular metals, we attempted to synthesize several cobalt complexes coordinated by TTF (tetrathiafulvalene)-type dithiolate ligands. We succeeded in the syntheses and structure determinations of ((n)Bu(4)N)(2)[Co(chdt)(2)](2) (1), ((n)Bu(4)N)(2)[Co(dmdt)(2)](2) (2), [Co(dmdt)(2)](2) (3), and [Co(dt)(2)](2) (4) (chdt = cyclohexeno-TTF-dithiolate, dmdt = dimethyl-TTF-dithiolate, and dt = TTF-dithiolate). Structure analyses of complexes 1-4 revealed that two monomeric [Co(ligand)2]- or [Co(ligand)(2)](0) units are connected by two Co-S bonds resulting in dimeric [Co(ligand)(2)](2)(2-) or [Co(ligand)(2)](2) molecules. Complex 1 has a cation-anion-intermingled structure and exhibited Curie-Weiss magnetic behavior with a large Curie constant (C = 2.02 K x emu x mol(-1)) and weak antiferromagnetic interactions (theta = -8.3 K). Complex 2 also has a cation-anion-intermingled structure. However, the dimeric molecules are completely isolated by cations. Complexes 3 and 4 are single-component molecular crystals. The molecules of complex 3 form two-dimensional molecular stacking layers and exhibit a room-temperature conductivity of sigmart = 1.2 x 10(-2) S.cm(-1) and an activation energy of E(a) = 85 meV. The magnetic behavior is almost consistent with Curie-Weiss law, where the Curie constant and Weiss temperature are 8.7 x 10(-2) K x emu x mol(-1) and -0.85 K, respectively. Complex 4 has a rare chair form of the dimeric structure. The electrical conductivity was fairly large (sigmart = 19 S.cm(-1)), and its temperature dependence was very small (sigma(0.55K)/sigma(rt) = ca. 1:10), although the measurements were performed on the compressed pellet sample. Complex 4 showed an almost constant paramagnetic susceptibility (chi(300) (K) = 3.5 x 10(-4) emu x mol(-1)) from 300 to 50 K. The band structure calculation of complex 4 suggested the metallic nature of the system. Complex 4 is a novel single-component molecular conductor with a dimeric molecular structure and essentially metallic properties down to very low temperatures.

Multicentric reticulohistiocytosis associated with ovarian cancer.

Multicentric reticulohistiocytosis (MR) is an uncommon disease characterized by joint and cutaneous manifestations. The diagnosis must be confirmed by histological evidence of typical histiocytes and multinucleated giant cells. Many conditions, including malignancy, have been described in association with MR. We herein report a female case of MR in whom partial improvement was obtained by steroid and low-dose methotrexate treatments. However, ovarian cancer was found and therefore a surgical resection and chemotherapy were performed. These treatments resulted in the complete resolution of the skin and joint symptoms. These findings support the close linkage between MR and malignancy and the efficacy of cytotoxic drugs for the treatment of MR.

Magnetic transitions of single-component molecular metal [Au(tmdt)2] and its alloy systems.

A single-component molecular conductor [Au(tmdt)2] (tmdt = trimethylenetetrathiafulvalenedithiolate) undergoes an antiferromagnetic phase transition at unprecedentedly high temperature (TN = 110 K). Black microcrystals of alloys, [Ni1-xAux(tmdt)2] (0.0 < x < 1.0) were prepared. The Au-rich system exhibited an antiferromagnetic transition. Metallic single crystal was obtained for x = 0.25.

Syntheses, structures, and physical properties of nickel bis(dithiolene) complexes containing tetrathiafulvalene (TTF) units.

To contribute to the development of single-component molecular metals, several nickel complexes with cyclohexeno-condensed or ethylenedioxy-substituted TTF (tetrathiafulvalene) dithiolate ligands, (R(4)N)(n)[Ni(chdt)(2)] [R = Me, n = 2 (1); R = (n)Bu, n = 1 (2); n = 0 (3)] and (R(4)N)(n)[Ni(eodt)(2)] [R = Me, n = 2 (4); R = (n)Bu, n = 1 (5); n = 0 (6)], were prepared. X-ray structures were determined on the monoanionic species 2 and 5. The tetra-n-butylammonium complex of the monoanionic [Ni(chdt)(2)] (2) with a 1:1 composition revealed that its magnetic susceptibility gave a good agreement with the Bonner-Fisher model (J/k(B) = -28 K), which was derived from the one-dimensional chains of anions with a regular interval. On the other hand, the magnetic susceptibility of the tetra-n-butylammonium complex of the monoanionic [Ni(eodt)(2)] (5) showed the Curie-Weiss behavior (C = 0.376 K.emu.mol(-1) and Theta = -4.6 K). Both of the monoanionic species 2 and 5 indicate that they belong to the S = 1/2 magnetic system and have relatively large and anisotropic g-values, suggesting the contribution of the nickel 3d orbital. Electrical resistivity measurements were performed on the compressed pellets of the neutral species 3 and 6. Fairly large conductivities were obtained (sigma(rt) = 1-10 S.cm(-1)). In addition, despite the measurements on the compressed pellets of powder samples, the neutral species 6 showed metallic behavior down to ca. 120 K and retained high conductivity even at 0.6 K [sigma(0.6 K)/sigma(rt) approximately 1/30], suggesting the crystal to be essentially metallic down to very low temperature. The electrical behavior and Pauli paramagnetism of 6 indicate the system to be a new single-component metal.

An indication of magnetic-field-induced superconductivity in a bifunctional layered organic conductor, kappa-(BETS)(2)FeBr(4).

Hybrid systems consisting of the conducting layers of organic donor molecules and the magnetic layers of inorganic anions have been focused on as possible bifunctional materials, whose conducting properties can be tuned by controlling the magnetic state of the anion layers on an application of magnetic field. Here we report the magnetoresistance of the antiferromagnetic organic superconductor, kappa-(BETS)2FeBr4 [BETS = bis(ethylenedithio)tetraselenafulvalene], consisting of the two-dimensional superconducting layers of the BETS semications and the insulating layers of the FeBr4- anions. Due to the metamagnetic nature of the Fe3+ spin system, characteristic resistivity decrease was observed just below the antiferromagnetic superconductor-to-ferromagnetic metal transition at 1.6 T. Furthermore, an indication of the onsets of the magnetic-field-induced superconductivity was discovered around 12.5 T.

Dual-action molecular superconductors with magnetic anions.

Dual-action organic superconductors, whose conducting properties can be sharply controlled by an external magnetic field, have been discovered in systems consisting of organic conduction layers based on bis(ethylenedithio)tetraselenafulvalene (BETS) molecules and magnetic anions. Owing to the metamagnetic nature of the anion layers, the superconducting state of kappa-BETS2FeBr4 can be switched on or off by applying the external field. In lambda-BETS2Fe0.4Ga0.6Cl4, exhibiting a field-induced superconducting transition for the field parallel to the conduction plane, the insulating, metallic, and superconducting states can be realized in a stepwise manner by slightly tuning the external magnetic field.

Magnetic molecular conductors based on BETS molecules and divalent magnetic anions [BETS = bis(ethylenedithio)tetraselenafulvalene].

Several conducting salts based on BETS [where BETS = bis(ethylenedithio)tetraselenafulvalene] molecules and divalent magnetic anions such as the (CoCl(4))(2-), (CoBr(4))(2-), and (MnBr(4))(2-) were prepared. Electrocrystallization by using the (CoCl(4))(2-) anion gave two kinds of crystals. Block-shaped crystals were cleared to be (BETS)(2)CoCl(4), which is an insulator with the high-spin state of cobalt 3d spin. On the other hand, the X-ray crystal structure analysis of a plate-shaped crystal of the (CoCl(4))(2-) salt revealed the system to be kappa-(BETS)(4)CoCl(4)(EtOH), which is metallic down to 0.7 K. The electronic band structure calculation gave a typical two-dimensional cylindrical Fermi surface. However, there is only very weak antiferromagnetic interaction between the S = 3/2 cobalt 3d spins because of its anion-solvent-intermingled layer structure. On the other hand, the electrocrystallization by using the (MnBr(4))(2-) anion yielded the plate-shaped black crystals of the (MnBr(4))(2-) salt. Crystal structure analysis of the (MnBr(4))(2-) salt showed that the salt is theta;-(BETS)(4)MnBr(4)(EtOH)(2) with alternating donor and anion-solvent mixed layers. The stacking direction in one donor layer is perpendicular to those of the neighboring layers. The electrical and magnetic properties of the theta;-(BETS)(4)MnBr(4)(EtOH)(2) salt showed the metallic behavior down to approximately 30 K and the paramagnetism of the high-spin manganese 3d spins. Band structure calculation of this salt gave an elliptical cylindrical Fermi surface. Because the Fermi surfaces of the adjacent donor layers are rotated to each other by 90 degrees, the theta-(BETS)(4)MnBr(4)(EtOH)(2) salt becomes a two-dimensionally isotropic metal.

Infrared electronic absorption in a single-component molecular metal.

The infrared spectra of the crystal of transition metal complex molecules with extended-TTF ligands, Ni(tmdt)2, which is the first single-component molecular metal that has a stable metallic state even at low temperatures, exhibited an extremely low-energy electronic absorption around 2200 cm-1 (tmdt = trimethylenetetrathiafulvalenedithiolate). The systematic shift of the absorption peaks for molecules similar to Ni(tmdt)2, which range from metallic to semiconducting crystals, shows that the single-component molecular conductors are composed of molecules with unprecedentedly small HOMO-LUMO gaps.

Highly conducting crystals based on single-component gold complexes with extended-TTF dithiolate ligands.

Highly conducting crystals based on single-component gold complexes with extended-TTF dithiolate ligands [Au(dmdt)(2)](0+) (1) and [Au(tmdt)(2)](0+) (2) were prepared (dmdt = dimethyltetrathiafulvalenedithiolate and tmdt = trimethylenetetrathiafulvalenedithiolate). On the basis of the synchrotron radiation powder diffraction data, the MEM electron density of 2 was successfully obtained. The conductivities of compacted powder samples of 1 and 2 at room temperature were 12 and 15 S cm(-1), respectively. Pauli-like susceptibility of 1 suggested the system to be essentially metallic at least above 50 K, while 2 showed a magnetic transition around 100 K without loss of its high conductivity.