Low-magnetic field effect and electrically detected magnetic resonance measurements of photocurrent in vacuum vapor deposition films of weak charge-transfer pyrene/dimethylpyromellitdiimide (Py/DMPI) complex.

Magnetic field effect (MFE) and electrically detected magnetic resonance (EDMR) measurements of photocurrent have been conducted to clarify the excited-state dynamics in films of an organic weak charge-transfer (CT) complex, Pyrene/Dimethylpyromellitdiimide (Py/DMPI), fabricated by vacuum vapor deposition. Low-field MFE measurements of the photocurrent were carried out using an interdigitated platinum electrode made on a quartz substrate as well as the re-examination of the photocurrent and MFE in the range of 3-200 mT. The spin-dependent carrier dynamics leading to the low-field MFE are reasonably simulated as the low-field effect due to the hyperfine mechanism in the radical-pair intersystem crossing, which was solved through the Liouville equations of the density matrix for the stepwise hopping model in the doublet electron-hole pair (DD pair mechanism). Single-crystal time-resolved electron spin resonance measurement was also carried out to justify the MFE mechanism. The averaged trap depth (Etrap) of the triplet exciton was estimated to be +640 ± 89 cm-1 (Etrap/kB = +921 ± 128 K) by the temperature dependence of the signal intensity. This finding gave confidential experimental evidence for the majority of the trapped triplet exciton (3ext). The EDMR experiment directly revealed the evidence of the weakly coupled electron-hole pairs. The effective activation energies (ΔE) for the separation from the photoinduced CT state to the mobile carries are 1200-1900 cm-1 (ΔE/kB = 1700-2700 K). A systematic protocol to clarify the photo-generated carrier dynamics in weak CT complexes is demonstrated, and our findings from this method give not only further support for the two types of collision mechanisms assumed in our previous work but also the detailed information of the carrier dynamics of the weak CT complex, including the activation energy and trapping/detrapping process, which have significant influence on the performance of the organic devices.

Extremely large magnetoresistance in the nonmagnetic metal PdCoO2.

Extremely large magnetoresistance is realized in the nonmagnetic layered metal PdCoO(2). In spite of a highly conducting metallic behavior with a simple quasi-two-dimensional hexagonal Fermi surface, the interlayer resistance reaches up to 35,000% for the field along the [11[over ¯]0] direction. Furthermore, the temperature dependence of the resistance becomes nonmetallic for this field direction, while it remains metallic for fields along the [110] direction. Such severe and anisotropic destruction of the interlayer coherence by a magnetic field on a simple Fermi surface is ascribable to orbital motion of carriers on the Fermi surface driven by the Lorentz force, but seems to have been largely overlooked until now.

Uniaxial strain orientation dependence of superconducting transition temperature (Tc) and critical superconducting pressure (Pc) in ß-(BDA-TTP)2I3.

Dependence of the superconducting transition temperature (T(c)) and critial superconducting pressure (P(c)) of the pressure-induced superconductor ß-(BDA-TTP)(2)I(3) [BDA-TTP = 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene] on the orientation of uniaxial strain has been investigated. On the basis of the overlap between the upper and lower bands in the energy dispersion curve, the pressure orientation is thought to change the half-filled band to the quarter-filled one. The observed variations in T(c) and P(c) are explained by considering the degree of application of the pressure and the degree of contribution of the effective electronic correlation at uniaxial strains with different orientations parallel to the conducting donor layer.

Observation and simulation of all angular magnetoresistance oscillation effects in the quasi-one-dimensional organic conductor (DMET)(2)I(3).

Measurements and calculations of magnetotransport in the organic conductor (DMET)(2)I(3) detect and simulate all angular magnetoresistance oscillations known for quasi-one-dimensional conductors. By employing the actual triclinic crystal structure in the calculations, these results address the putative vanishing of the primary magnetoresistance phenomenon, the Lebed magic angle effect, for orientations in which it was expected to be strongest. They also show a common origin for Lebed and the so-called Lee-Naughton oscillations and confirm the generalized nature of angular effects in such systems.

A new organic superconductor, (DODHT)2BF4 x H2O.

In addition to two organic superconductors (DODHT)2X [DODHT = (1,4-dioxane-2,3-diyldithio)dihydrotetrathiafulvalene; X = PF6 and AsF6] previously reported by us, the BF4 salt of DODHT containing one water molecule [(DODHT)2BF4 x H2O] has been found to undergo a superconducting transition at 3.2 K under a hydrostatic pressure of 15.5 kbar.

Pressure transmitting medium Daphne 7474 solidifying at 3.7 GPa at room temperature.

A pressure transmitting medium named Daphne 7474, which solidifies at P(s)=3.7 GPa at room temperature, is presented. The value of P(s) increases almost linearly with temperature up to 6.7 GPa at 100 degrees C. The high pressure realized by a medium at the liquid state allows a higher limit of pressurization, which assures an ideal hydrostatic pressure. We show a volume change against pressure, pressure reduction from room to liquid helium temperature in a clamped piston cylinder cell, pressure distribution and its standard deviation in a diamond anvil cell, and infrared properties, which might be useful for experimental applications.

A metallic (EDT-DSDTFVSDS)2.FeBr4 salt: antiferromagnetic ordering of d spins of FeBr4- ions and anomalous magnetoresistance due to preferential pi-d interaction.

The 2:1 salt of a new donor molecule, EDT-DSDTFVSDS with FeBr4- ion, (EDT-DSDTFVSDS)2.FeBr4 showed an essentially metallic behavior despite a small upturn in the electrical resistance below ca. 30 K (electrical conductivities at 290 and 4.2 K are 200 and 170 S cm-1, respectively). The Fe(III) d spins of the FeBr4- ions in this salt were subject to antiferromagnetic ordering at 3.3 K by virtue of a strong pi-d interaction (Jpid) which is comparable to that in a molecular metallic conductor, lambda-(BETS)2.FeCl4, and of a very weak d-d interaction (Jdd). This strong pi-d interaction was evidenced by a large and negative magnetoresistance effect (ca. 20% at 5 T) as well as by the appearance of a large dip in the resistance at the magnetic field (ca. 2.0 T) parallel to the easy axis for the spin-flop transition of the Fe(III) d spins.

Electrical conducting and magnetic properties of (ethylenedithiotetrathiafulvalenothioquinone-1,3-diselenolemethide)2.FeBr4 (GaBr4) crystals with two different interlayer arrangements of donor molecules.

Two donor molecules newly synthesized, dimethylthio- and ethylenedithio-tetrathiafulvalenothioquinone-1,3-diselenolemethides (1 and 2), were used to prepare their charge-transfer (CT) salts with a magnetic FeBr(4)(-) counteranion. For 1, a low electrical conducting 1:1 salt (1.FeBr(4)) was obtained, in which molecules of 1 are tightly dimerized in a one-dimensional (1D) stacking column. On the other hand, 2 gave a 2:1 salt (2(2).FeBr(4)) as two different kinds of plate crystals (I and II). Both I and II possess similar stacking structures of molecules of 2 in each 1D column with a half-cut pipelike structure along the c axis. However, for I, the stacking columns are aligned in the same direction along the a and b axes, while for II they are in the same direction along the a axis, but in the reverse direction along the b axis, resulting in the difference in the relative arrangement of molecules of 2 and FeBr(4)(-) ions between the two crystals. The room-temperature electrical conductivities of the single crystals of I and II were 13.6 and 12.7 S cm(-)(1), respectively. The electrical conducting behavior in I was metallic above 170 K but changed to be semiconducting with a very small activation energy of 7.0 meV in the temperature range 4-170 K. In contrast, II showed the semiconducting behavior in the whole temperature range 77-285 K. The corresponding nonmagnetic GaBr(4)(-) salts with almost the same crystal structure as I and II showed definitively different electrical conducting properties in the metal to semiconductor transition temperature in I as well as in the magnitude of activation energy in the semiconducting region of I and II. The interaction between the d spins of FeBr(4)(-) ions was weak and antiferromagnetic in both I and II, but the magnitude of the spin interaction was unexpectedly larger compared with that in the FeBr(4)(-) salt of the corresponding sulfur derivative of 2 with closer contact between the neighboring FeBr(4)(-) ions. These electrical conducting and magnetic results suggest a significant interaction between the conducting pi electrons and the d spins of FeBr(4)(-) ions located near the columns or layers.

New organic superconductors consisting of an unprecedented pi-electron donor.

The synthesis and electrochemical properties of a new organic donor, (1,4-dioxan-2,3-diyldithio)dihydrotetrathiafulvalene (DODHT), and the crystal structures and physical properties of its superconducting salts are described. The DODHT molecule has the bulky dioxane ring condensed by cis fusion, and the reduced pi-electron system of DODHT, as compared with conventional tetrachalcogenafulvalene donors, leads to both the weak electron-donating ability and the large on-site Coulomb energy. Nevertheless, DODHT produces the superconducting AsF6 and PF6 salts, which are isostructural and exhibit superconducting transitions at 3.3 and 3.1 K, respectively, under 16.5 kbar.

Metallic conductivity and ferromagnetic interaction of iron(III) d spins in the needle crystals of (ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)(2).FeBr(4) salt.

The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.