Akihiro Otsuka

Crystal structures and physical properties of cation radical salt (C1 TET-TTF)2PF6 and related salts

Abstract Two kinds of new conducting crystals of C1 TET-TTF (where C1 TET-TTF is bis(methylthio)ethylenedithiotetrathiafluvalene) with PF6 were prepared by electrocrystallization in MeOH and EtOH. The salt obtained from MeOH crystallizes in the triclinic crystal system and space group P 1 ; a = 15.859(4), b = 11.601(4), c = 4.880(5) A , α = 100.12(5), β = 92.53(5), γ = 72.51(2)°, V = 843(1) A 3 , and Z = 1. The noncentrosymmetric donor molecules stack in parallel so that the methylthio groups align on the same side within a molecular column in spite of its lowered symmetry. The S⋯S contact distances (3.54–3.68 A) are shorter than the sum of the van der Waals radii in the transverse direction. Both kinds of crystals from MeOH and EtOH showed approximately the same lattice constants, angular dependences of g values around the c axis (2.005–2.011), and resistivities (10−1 Ω cm) at room temperature. The crystals from MeOH gave satellite reflections along the c axis mainly as a result of anion disorder, and yielded EPR linewidth of 28 G at room temperature. In contrast, for the crystals from EtOH, no satellite reflections and linewidth of 25 G at room temperature were observed. Temperature dependence of resistivity was small in both cases, and showed metallic behavior from room temperature down to about 220 K for the crystals from MeOH and down to about 40 K for those from EtOH.

C1 TET-TTF salts with octahedral anions

Abstract A hybrid molecule between BEDT-TTF and TTC 1 -TTF (tetrakis(methylthio)-TTF; C 1 TET-TTF (bis(methylthio)ethylenedithio-TTF), gave cation radical salts with PF 6 , AsF 6 , and Sb 2 F 11 anions. Two PF 6 and two AsF 6 salts were electrochemically prepared in methanol or ethanol, and all of the four showed metallic temperature dependence of d.c. resistivity at around room temperature. These four salts are isomorphic, however, there are slight differences in the anion arrangement which is dependent on the solvent used. The salts from ethanol gave narrower EPR line widths than those from methanol at r.t.. The temperature dependence of EPR intensity for the four salts showed a similar fashion to one another, though the four-probe resistivity measurements exhibited a variety of temperature dependences. Unexpectedly, the Sb 2 F 11 salt was obtained by the electrolysis with TBA·SbF 6 in methanol, and showed semiconducting behavior. The composition was (C 1 TET-TTF) 4 Sb 2 F 11 with a binuclear anion of two Sb centered octahedra sharing a F atom.

CCDC 984332: Experimental Crystal Structure Determination

Related Article: Manabu Ishikawa, Yoshiaki Nakano, Mikio Uruichi, Akihiro Otsuka, Kyuya Yakushi, Hideki Yamochi|2014|Eur.J.Inorg.Chem.||3941|doi:10.1002/ejic.201400128

CCDC 984329: Experimental Crystal Structure Determination

Related Article: Manabu Ishikawa, Yoshiaki Nakano, Mikio Uruichi, Akihiro Otsuka, Kyuya Yakushi, Hideki Yamochi|2014|Eur.J.Inorg.Chem.||3941|doi:10.1002/ejic.201400128

CCDC 984331: Experimental Crystal Structure Determination

Related Article: Manabu Ishikawa, Yoshiaki Nakano, Mikio Uruichi, Akihiro Otsuka, Kyuya Yakushi, Hideki Yamochi|2014|Eur.J.Inorg.Chem.||3941|doi:10.1002/ejic.201400128

CCDC 984330: Experimental Crystal Structure Determination

Related Article: Manabu Ishikawa, Yoshiaki Nakano, Mikio Uruichi, Akihiro Otsuka, Kyuya Yakushi, Hideki Yamochi|2014|Eur.J.Inorg.Chem.||3941|doi:10.1002/ejic.201400128

CCDC 1465068: Experimental Crystal Structure Determination

Related Article: Dmitri V. Konarev, Alexey V. Kuzmin, Yoshiaki Nakano, Salavat S. Khasanov, Manabu Ishikawa, Akihiro Otsuka, Hideki Yamochi, Gunzi Saito, Rimma N. Lyubovskaya|2016|Dalton Trans.|45|10780|doi:10.1039/C6DT01132B