Polyhedron p. 2513 - 2521 (2005)
Update date:2022-07-30
Topics:
Mukai, Kazuo
Shiba, Daisuke
Mukai, Kyohei
Yoshida, Kenji
Hisatou, Hiroyuki
Ohara, Keishi
Hosokoshi, Yuko
Azuma, Nagao
Five kinds of (1:1) and (1:3) salts of 3-(4- and 3-alkyl-pyridinium)-1,5- diphenylverdazyl (alkyl = ethyl and methyl) radical cations with Ni(dmit) 2 anion ([p-EtPyDV]+[Ni(dmit)2]- (1), [m-EtPyDV]+[Ni(dmit)2]- (2), [p-MePyDV]+[Ni(dmit)2]- (3), [m-MePyDV] +[Ni(dmit)2]- (4), and [p-MePyDV]+[Ni(dmit)2]3- (5)) (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) have been prepared, and the magnetic susceptibilities (χM's) have been measured between 1.8 and 300 K. The χM of salt 1 can be well explained by a four-spin linear tetramer model ([p-EtPyDV]+-[Ni(dmit)2] --[Ni(dmit)2]--[p-EtPyDV]+) with an end exchange interaction 2J1/kB = -780 K and a central interaction 2J2/kB = -200 K. The formation of magnetic tetramer in salt 1 has been ascertained by the crystal structure analysis of 1. The χM of salt 2 was explained by the sum of the contributions from: (i) a dimer system (2J/kB = -320 K) due to Ni(dmit)2 anions and (ii) the one-dimensional (1D) Heisenberg ferromagnetic linear-chain system (2J kB = +2.5 K) due to verdazyl cations. The χM of salt 3 is similar to that of salt 1, suggesting a formation of magnetic tetramer in salt 3. The χM of salt 4 shows a broad maximum at Tmax = 100 ± 2 K, and can be explained by a 1D Heisenberg antiferromagnetic alternating-chain model with 2J1/k B = -165 K (alternation parameter α = J2/J 1 = 0.6). The conductivity (σ) of salts 1, 2, 3 and 4 at 293 K was σ = 2.3 × 10-5, 1.1 × 10-3, 1.4 × 10-5 and 5.4 × 10-6 S cm-1 with an activation energy of EA = 0.28, 0.52, 0.21 and 0.33 eV, respectively. The (1:3) salt 5 (σ = 1.0 S cm-1, EA = 0.048 eV) showed three to five orders of magnitude higher conductivity than those of the (1:1) salts 1-4 at room temperature. All the (1:1) and (1:3) salts 1-5 are new molecular paramagnetic semiconductors.
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