FT-IR investigations of BEDO-TTF and radical salts of BEDO-TTF

We investigated powder absorption spectra of the donor BEDO-TTF and some radical salts of BEDO-TTF, which are metals even at low temperatures. After an assignment of the bands in the neutral donor we found in the radical salts different vibrational frequencies of bands correlated with C-O vibrations. These frequencies are directly related to the average charge on the donor molecule. Additionally frequencies of CH2-stretching vibrations exhibit differences, which can be ascribed to a varying strength of donor-anion interaction depending on the respective anion

The double-stack structure of di(3,4-ethylenedithio-3',4'-dimethyl-2,2',5,5'-tetrathiafulvalenium)perchlorate, (DIMET)2ClO4

2C10H10S6 1/2+.ClO-4 , M r= 744·62, triclinic, PI, α=7·000 (2), b =7·824 (3), c = 27·010 (14) A, α = 88· 10 (4), β= 89·02 (4), Y = 74· 58 (3)°, V = 1425 A 3, Z=2, Dx=1·73gcm-3, λ( MoKa) = 0·7107 A, μ= 10·1 cm-1, F(000) = 762, room temperature, final R = 0.063 for 3076 observed independent reflections. Two crystallographically independent DIMET molecules each with an average charge of ½+ form stacks, which run nearly perpendicularly to one another. Within each stack, two different interplanar spacings between adjacent parallel molecules are found. These overlap patterns are similar to those found in tetrahydrofuran solvate. The stacks are arranged side by side perpendicular to the long molecular axis to give a sheet-like arrangement

Superconductivity at 10 K and ambient pressure in the organic metal (BEDT-TTF)2Cu(SCN)2

We confirm the observation of superconductivity at ambient pressure above 10 K in the organic metal (BEDT-TTF)2Cu(SCN)2 as reported recently by Urayama et al [12]. In addition we have measured ESR, ac-susceptibility and thermopower in crystals of (BEDT-TTF)2Cu(SCN)2 and have shown that in contrast to other organic superconductors here a relatively sharp superconducting transition even in the ac-susceptibility can be observed which saturates already around 8 K. The thermopower measurements indicate a clear metal-metal phase transition at 100 K and a possible second phase transition at around 50 K, while from the temperature dependence of the resistivity and susceptibility (ESR) these phase transitions cannot be observed

Preparation, structure and physical properties of BEDT-TTF nitrates

Electrocrystallization of BEDT-TIF in THF with tetrabutylammonium nitrate as supporting electrolyte leads to the deposition of at least three different phases. Sheets of BEDT-TTF radical cations with short intermolecular S···S contacts (>3.315(4) A) are separated by anion layers. Two more BEDT-TrF nitrates have been characterized by their unit cell data. Resuhs of temperature dependent electrical conductivity and thermopower measurements on crystals of the a-phase are presented. They are metallic down to about 30 K

Preparation, structure and investigations of BEDT-TTF trihalides

Crystals of the β-phases of (BEDT-TTF)2Br-I-Br (1) and (BEDT-TTF)2I-I-Br (2) have been isolated by electrocrystallization. The solids can be obtained using different tetrabutylammonium trihalides containing iodine and bromine as supponing electrolytes. Cyclovoltammetric results show clearly that the trihalide anions are involved in the oxidation reactions near the anode which finally lead to the crystals

Radical cation salts of an unsymmetrical BEDT-TTF derivative: molecular structure and physical properties of (DIMET)2ClO4xTHF

Sheets of cations with an average charge of 1/2+ are separated by sheets of anions and THF solvent molecules. Intermolecular S···S contacts result in two-dimensional physical properties. Electrical conductivity and thermopower measurements indicate two broad phase transitions at around 200 K and 80 K

(BEDO-TTF)2ReO4·(H2O): a new organic superconductor

The structure and the temperature dependence of the resistivity, thermopower and ac-susceptibility of the new organic metal (BEDO-TTF)2ReO4(H2O) was investigated. The resistivity and thermopower data indicate phase transitions at 213K, around 90K and 35K. Below 2.5K an onset to superconductivity is observed in the resistivity data. Superconductivity was suppressed in the resistivity at 1.3K by applying a magnetic field of about 0.2T. Ac-susceptibility data indicate that superconductivity is a bulk effect in (BEDO-TTF)2ReO4(H2O) but the onset for superconductivity observed in the ac-susceptibility is only at 0.9K and the transition seems to be complete only at temperatures below 50 mK. This broad transition might be due to some disorder in the structure created by the low temperature phase transitions

Radical cation salts of an unsymmetrical BEDT-TTF derivative: DIMET

A surprising fact in the structures of the organic superconductors (TMTSF)2 Cl04 and -β-(BEDT-TTF)2X (X=I3-, IBr2- and AuI2-) is that there exists a slight dimerisation of the donor molecules within the stacks of these radical cation salts. Therefore, the question arises whether a more pronounced dimerisation in organic radical salts of this type leads to stronger intra- and interstack interactions and to stronger couplings between the unpaired electrons. This might result in an increase of the transition temperature to superconductivity. A step in this direction is the preparation of "unsymmetrical" donors like DIMET, which was synthesized recently. This new donor was electrocrystallized by us in different solvents using tetrabutylammonium salts of various anions like ClO4-, ReO4-, NO3-, I3-, (AuI2)-, PF6-, ASF6- and SbF6- as electrolytes. With all these anions radical salts were obtained and in some cases even several crystallographic different phases

Transport properties of single crystals and polycristalline pressed samples of (BEDT-TTF)2X salts and related coordination polymers

Ten years ago in 1979, superconductivity was observed for the first time in an organic metal. today, about 30 different organic metals are known, which become superconducting under pressure or ambient pressure. The organic superconductors with the highest transition temperatures are all radical salts of the donor bis(ethylenedithioio)-tettathiafulvalene (BEDT-TTF), namely at ambient pressure (BEDT-TTF)2CU(NCS)2 (Tc = 10.4 K) and αt,-(BEDT-TTF)2I3 (Tc = 8 K) and under isotropic pressure β H- (BEDT-TTF)2I3(0.5 kbar, Tc = 7.5 K) The latter β H-phase can even become superconducting at 8 K and ambient pressure, after a special pressure-temperature cycling procedure i.e. pressurization up to 1 kbar at room temperature, and release of the helium gas pressure at temperarures below 125 K. Nevertheless, this superconducting state at 8 K in β H-(BEDT -TTF)2I3 is only metastable , since warming up the crystal above 125 K and cooling down again under ambient pressure, results only in superconductivity at 1.3 K, the so-called β L - or β-phase

NMR investigations of the organic metals and superconductors α-(BEDT-TTF)2I3, β-(BEDT-TTF)2I3 and α t-(BEDT-TTF)2I3

1H and 13C spin lattice relaxation rates as well as 13C Knight shifts of the quasi two dimensional organic metals α-, β- and αt-(BEDT-TTF)2I3 are reported. In β- and αt-(BEDT-TTF)2I3 at temperatures below 100 K the Korringa relation is fulfilled. Near the critical temperature of 8K of the stable superconducting state of αt-(BEDT-TTF)2I3 an enhancement of the proton spin lattice relaxation rate due to superconducting fluctuations is observed. The observed individual 13C Knight shifts, as measured by magic angle sample spinning and cross polarisation methods range between -6 and +244 ppm for α- phase and -10 and +125 ppm for β- and αt- phase crystals