1. Genuine organic magnetic semiconductors: electrical and magnetic properties of the TCNQ and iodide salts of methylpyridinium-substituted verdazyl radicals
- Author
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Katsuya Inoue, Nagao Azuma, Yasuo Shimobe, Kazuo Mukai, Masateru Taniguchi, Kazuyoshi Tanaka, Yuko Hosokoshi, Syunsuke Jinno, and Yohji Misaki
- Subjects
chemistry.chemical_classification ,Magnetic moment ,Chemistry ,Stereochemistry ,Dimer ,Iodide ,General Chemistry ,Magnetic semiconductor ,Magnetic susceptibility ,Ion ,chemistry.chemical_compound ,Crystallography ,Materials Chemistry ,Antiferromagnetism ,Curie constant - Abstract
Two kinds of iodide salts of 3-(4- and 3-methylpyridinium)-1,5-diphenylverdazyl radical cations ([p-MePyDV]+I− (1) and [m-MePyDV]+I− (2)) and four kinds of 1 ∶ 1 and 1 ∶ 2 salts of the same verdazyl radical cations with tetracyanoquinodimethanide (TCNQ) anion ([p-MePyDV]+[TCNQ]− (3), [m-MePyDV]+[TCNQ]− (4), [p-MePyDV]+[TCNQ]2− (5), and [m-MePyDV]+[TCNQ]2− (6)) have been prepared, and the magnetic susceptibilities (χM’s) have been measured between 1.8 and 300 K. Salts (1) and (2) behave as one-dimensional (1D) alternating and nonalternating Heisenberg antiferromagnets with exchange interactions of 2JI-II/kB = −171 ± 4 K (alternation parameters α = JI-III/JI-II = 0.5) and 2J/kB = −15.4 ± 0.9 K (α = 1), respectively. The χM of (3) follows the Curie–Weiss law with a Curie constant of 0.365 K emu mol−1 and a positive Weiss constant of +2.1 ± 0.2 K, indicating disappearance of a net magnetic moment due to the formation of strong spin pairs in TCNQ anion molecules. The χM of (4) shows a broad maximum at Tmax = 24 ± 1 K. The χM can be well reproduced by the sum of the contributions from i) a 1D Heisenberg antiferromagnetic alternating-chain system with 2J1/kB = −47 ± 2 K (α = J2/J1 = 0.9) and ii) a dimer system with 2J/kB = −636 ± 30 K. The susceptibilities of (5) and (6) showed anomalous magnetic behavior that cannot be explained by a simple model. The separate contributions of the verdazyl cation and TCNQ anion subsystems to the total magnetic susceptibility of the salts were evaluated from measurements of the temperature dependence of the g-value. The 1 ∶ 1 salts (3) and (4) are insulators. On the other hand, the pressed pellet conductivity (σ) of the 1 : 2 salts (5) and (6) at 20 °C was σ = 8.1 × 10−3 and 2.9 × 10−2 S cm−1 with activation energy of EA = 0.092 ± 0.005 and 0.091 ± 0.005 eV, respectively. The two 1 ∶ 2 salts (5) and (6) are new genuine organic magnetic semiconductors.
- Published
- 2003