Metal-semiconductor structural phase transitions and antiferromagnetic orderings in (Benzo-TTFVO)2•MX4 (M = Fe, Ga; X = Cl, Br) salts

被引:8
|
作者
Hiraoka, Takashi
Fujiwara, Hideki [1 ]
Sugimoto, Toyonari
Nakazumi, Hiroyuki
Noguchi, Satoru
Kuribayashi, Akihiro
Ishida, Takekazu
Yokogawa, Keiichi
Murata, Keizo
Mori, Takehiko
Aruga-Katori, Hiroko
Kimura, Shojiro
Hagiwara, Masayuki
机构
[1] Osaka Prefecture Univ, Grad Sch Sci, Dept Chem, Osaka 5998570, Japan
[2] Osaka Prefecture Univ, Grad Sch Engn, Dept Appl Chem, Osaka 5998531, Japan
[3] Japan Sci & Technol Agcy, CREST, Saitama 3220012, Japan
[4] Osaka Prefecture Univ, Grad Sch Engn, Dept Phys & Elect, Osaka 5998531, Japan
[5] Osaka City Univ, Grad Sch Sci, Dept Mol Mat Sci, Osaka 5588585, Japan
[6] Tokyo Inst Technol, Grad Sch Sci & Engn, Dept Organ & Polymer Mat, Tokyo 1528552, Japan
[7] RIKEN, Inst Phys & Chem Res, Saitama 3510198, Japan
[8] Osaka Univ, KYOKUGEN, Osaka 5608531, Japan
关键词
CHARGE-TRANSFER SALTS; FIELD-INDUCED SUPERCONDUCTIVITY; D-SPINS; ORGANIC CONDUCTORS; CRYSTAL-STRUCTURES; BEDT-TTF; DONOR; BETS; CR; KAPPA-(BETS)(2)FEBR4;
D O I
10.1039/b612053a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Crystals of the 2 : 1 salts of a new donor molecule, benzotetrathiafulvalenoquinone-1,3-dithiolemethide ( 4, Benzo-TTFVO) with magnetic FeX4- and non-magnetic GaX4- ( X = Cl, Br) ions, 4(2) center dot FeX4 and 4(2) center dot GaX4, are isostructural to each other and showed a beta-type packing of the donor molecules where they form a uniform-stacked structure with an interplanar distance of 3.50 angstrom. These salts exhibited metallic behavior down to 140 - 170 K, but at these temperatures (similar to TM-I) an abrupt increase in the resistivities (rho) occurred and thereafter semiconducting behavior with an activation energy of 40 - 100 meV was observed. A structural change in the donor column from uniform to tetramer-unit stacks was observed in the 4(2) center dot FeBr4 crystal before and after TM-I. By application of pressures up to 1.0 GPa, the metallic behavior in the higher temperature region was gradually strengthened and TM-I gradually became lower with increasing pressure, but the transitions could not be suppressed at all. In response to the metal semiconductor transition at TM-I, there was a sharp decrease in the paramagnetic susceptibility of the pi electron system, where the transition from Pauli paramagnetism due to the metal-conducting behavior to the spin singlet state caused by tetramer formation of the donor molecules was observed. In addition, the FeX4- ( X = Cl, Br) salts showed comparatively strong antiferromagnetic interactions between the Fe( III) d spins of the FeCl4- and FeBr4- ions ( Weiss temperature: -11 K for 4(2) center dot FeCl4 and -37 K for 4(2) center dot FeBr4), giving rise to antiferromagnetic orderings at 1.6 K for 4(2) center dot FeCl4 and 9.3 K for 4(2) center dot FeBr4. The magnitudes of the d - d and pi - d interactions in 4(2) center dot FeBr4 are calculated to be J(dd) = 2.06 K and J(pi d) = 2.32 K, respectively. The comparison of these J values with the other magnetic conductors based on our system suggests that the d - d interaction of 4(2) center dot FeBr4 is stronger than the pi - d interaction. Since the three-dimensional antiferromagnetic ordering appears at the comparatively high temperature of 9.3 K, there is an important contribution of the pi electrons to the antiferromagnetic ordering of the Fe( III) d spins in order to mediate the magnetic interaction between two-dimensional magnetic anion layers.
引用
收藏
页码:1664 / 1673
页数:10
相关论文
共 50 条
  • [1] Metallic/semiconducting behaviors and an antiferromagnetic ordering of FeBr4-_d spins in (Benzo-TTFVS)2.MX4 (M = Fe, Ga;: X = Cl, Br)
    Hiraoka, T
    Kamada, Y
    Matsumoto, T
    Fujiwara, H
    Sugimoto, T
    Noguchi, S
    Ishida, T
    Nakazumi, H
    Katori, HA
    JOURNAL OF MATERIALS CHEMISTRY, 2005, 15 (34) : 3479 - 3487
  • [2] Magnetoresistance effects evidencing the π-d interaction in metallic organic conductors, (EDT-DSDTFVO)2•MX4 (M = Fe, Ga; X = Cl, Br)
    Fujiwara, Hideki
    Hayashi, Toshiki
    Sugimoto, Toyonari
    Nakazumi, Hiroyuki
    Noguchi, Satoru
    Li, Lin
    Yokogawa, Keiichi
    Yasuzuka, Syuma
    Murata, Keizo
    Mori, Takehiko
    INORGANIC CHEMISTRY, 2006, 45 (15) : 5712 - 5714
  • [3] Gas phase structures of chalcogen tetrahalides MX4 with M = S, Se, Te and X = F, Cl, Br, I
    Oberhammer, Heinz
    Shlykov, Sergey A.
    DALTON TRANSACTIONS, 2010, 39 (11) : 2838 - 2841
  • [4] Gas Phase Properties of MX2 and MX4 (X = F, Cl) for M = Group 4, Group 14, Cerium, and Thorium
    Thanthiriwatte, K. Sahan
    Vasiliu, Monica
    Battey, Samuel R.
    Lu, Qing
    Peterson, Kirk A.
    Andrews, Lester
    Dixon, David A.
    JOURNAL OF PHYSICAL CHEMISTRY A, 2015, 119 (22): : 5790 - 5803
  • [5] Crystal structures, and electrical conducting and magnetic properties in the plate crystals of (Ethylenedithiotetrathiafulvalenoquinone-1, 3-dithiolemethide)2 • MX4 (M=Fe, Ga, X=Br; M=Fe, X=C1) salts
    Matsumoto, T
    Kominami, T
    Ueda, K
    Sugimoto, T
    Tada, T
    Yoshino, H
    Murata, K
    Shiro, M
    Negishi, E
    Matsui, H
    Toyota, N
    Endo, S
    Takahashi, K
    JOURNAL OF SOLID STATE CHEMISTRY, 2002, 168 (02) : 408 - 417
  • [6] REACTIONS OF HYDROGENATED THIAMINE DERIVATIVES WITH K2[MX4], WHERE M IS PDII OR PTII AND X IS CL OR BR
    HADJILIADIS, N
    MARKOPOULOS, J
    JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1981, (07): : 1635 - 1644
  • [7] New organic conductors based on dibromo- and diiodo-TSeFs with magnetic and non-magnetic MX4 counter anions (M = Fe, Ga; X = Cl, Br)
    Shirahata, Takashi
    Kibune, Megumi
    Maesato, Mitsuhiko
    Kawashima, Tomohito
    Saito, Gunzi
    Imakubo, Tatsuro
    JOURNAL OF MATERIALS CHEMISTRY, 2006, 16 (33) : 3381 - 3390
  • [8] Antiferromagnetic or canted antiferromagnetic orderings of Fe(III) d spins of FeX4- ions in BEDT-TTFVO(S)•FeX4 (X = Cl, Br) [BEDT-TTFVO(S) = bis(ethylenedithio)tetrathiafulvalenoquinone(-thioquinone)-1,3-dithiolemethide]
    Wang, Mingxing
    Xiao, Xunwen
    Fujiwara, Hideki
    Sugimoto, Toyonari
    Noguchi, Satoru
    Ishida, Takekazu
    Mori, Takehiko
    Katori, Hiroko Aruga
    INORGANIC CHEMISTRY, 2007, 46 (08) : 3049 - 3056
  • [9] Structures and properties of radical cation salts of novel tetraselenafulvalene derivatives (BPT-TSF, EDT-PT-TSF, and BEST-TSF) with MX4(M = Fe, Ga, X = Cl, Br)-type anions
    Kodani, M
    Murakami, S
    Jigami, T
    Takimiya, K
    Aso, Y
    Otsubo, T
    MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 2002, 376 : 47 - 52
  • [10] Structural and magnetic phase transitions in (Chloroanilinium)2CuX4 (X = Cl, Br)
    T. Asaji
    Applied Magnetic Resonance, 2004, 27 : 197 - 205