Strain-Induced Double Carbon-Carbon Bond Activations of Cycloparaphenylenes by a Platinum Complex: Application to the Synthesis of Cyclic Diketones.

The carbon-carbon (C-C) bond activation of [n]cycloparaphenylenes ([n]CPPs) by a transition-metal complex is herein reported. The Pt0 complex Pt(PPh3 )4 regioselectively cleaves two C-C σ bonds of [5] CPP and [6]CPP to give cyclic dinuclear platinum complexes in high yields. Theoretical calculations reveal that the relief of ring strain drives the reaction. The cyclic complex was further transformed into a cyclic diketone by using a CO insertion reaction.

Weak ferromagnetism in a semiconducting (ethylenedithiodiselena- dithiafulvalenoquinone-1,3-diselenolemethide)2.FeBr4 salt.

The 2:1 salts of a new bent donor molecule, ethylenedithiodiselenadithiafulvalenoquinone-1,3-diselenolemethide (EDT-DSDTFVODS) and either an FeBr(4)- or a GaBr(4)- ion exhibit semiconducting properties and had small activation energies. The Fe(III) d spins of the FeBr(4)- salt are initially subject to a strong antiferromagnetic interaction and afterward exhibited a weak ferromagnetism at 3.8 K with a very small remanent magnetization of ca. 4 x 10(-2) mu(B) and a spin-flop near 25 kOe along the intercolumnar direction.

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.

Magnetoresistance effects evidencing the pi-d interaction in metallic organic conductors, (EDT-DSDTFVO)2*MX4 (M = Fe, Ga; X = Cl, Br).

The 2:1 salts of a new donor molecule, EDT-DSDTFVO with MX4- (M = Fe, Ga; X = Cl, Br) ions, were prepared. The crystal structures of the donor molecules had a beta-type packing motif. All the salts essentially exhibited metallic behaviors despite the small upturns in the resistances below 30-70 K. A large negative magnetoresistance (MR) effect [-14.7% (rho(perpendicular)) at 4.0 K and 5 T] was observed in the FeCl4- salt, while a positive MR effect [+4.0% (rho(perpendicular)) at 4.0 K and 5 T] was observed in the GaCl4- salt, suggesting that there is a pi-d interaction in the FeCl4- salt. The pressure application suppressed the resistivity upturns, increased the negative MR effect (-17.7% at 9.5 kbar) in the FeCl4- salt, and decreased the positive MR effect (+3.3% at 15 kbar) in the GaCl4- salt.

Stable metallic behavior and antiferromagnetic ordering of Fe(III) d spins in (EDO-TTFVO)2.FeCl4.

We report the crystal structure and physical properties of the 2:1 FeCl4- salt of a new donor molecule, EDO-TTFVO. Crystal structure analysis of this salt revealed that the donor molecules formed a beta' '-type two-dimensional conducting layer, and there is a short S...Cl contact between the donor molecules and the FeCl4- ions, which is expected to mediate a strong pi-d interaction. This salt showed a stable metallic conducting behavior down to 0.3 K and an antiferromagnetic ordering at TN approximately 3.0 K, indicating that this salt becomes a new antiferromagnetic molecular metal at ambient pressure. The appearance of the magnetic ordering is considered to originate from the strong pi-d interactions between the donor molecules and the FeCl4- ions because the field dependence of magnetoresistances was remarkably affected below the antiferromagnetic transition temperature.