Phase Transition Mechanisms of BEDT-TTF Radical Ion Salts.
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概要
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The metal-insulator phase-transition mechanisms of the radical ion salts based on the organic donor BEDT-TTF are discussed, on the basis of the crystal structure and physical property measurements. In the case of (BEDT-TTF)3(ClO4)2, the thermal rotation of the anions in the crystal plays an important role in the emergence of the second-order structural phase transition at 171K, whereas the isomorphous (BEDT-TTF)3(HSO4)2 shows the first-order Mott-type transition at 126K and the structural transition is surpressed, as the consequence of the prohibition of the anion rotation by the hydrogen bonds between the anions. For the case of solvent containing salts, (BEDT-TTF)2X·TCE0.5 (X=ClO4, BF4; TCE=1, 1, 2-trichloroethane), the emergence of the structural phase transition at 25K (ClO4 salt) and 60K (BF4 salt) is strongly related to the cooling rate around 150-200K, at which the growth of the superstructure is observed. The low-temperature X-ray structure analysis reveals that the origin of this superstructure for the BF4 salt is the partial freezing of the thermally puckered dihydrodithiin rings attached to the TTF skeletons of the donor molecules.
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