Journal
INORGANIC CHEMISTRY
Volume 61, Issue 20, Pages 7754-7764Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c04004
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Funding
- JPSP KAKENHI [JP26410095, JP15H03798, JP19H02690, JP1905406, JP20H05621]
- Ehime University
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The synthesized TMTTP exhibits high electrical conductivity, with the anion shape and size of corresponding salts affecting the electrical properties. Different salts show metallic conductivity or metal-to-insulator transition at different temperatures, and single crystal structure analysis reveals a beta-type packing motif.
The tetramethyl derivative of bis-fused tetrathiaful-valene, 2,5-bis(4,5-dimethyl-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathia-pentalene (TMTTP), has been successfully synthesized. Most of the radical cation salts consisting of TMTTP feature a high electrical conductivity of Sigma rt=101to 102Scm-1on a single crystal. The anion shape and size of TMTTP conductors modulate the electrical properties. The PF6-and AsF6-salts exhibit metallic conductivity down to 10 K, while the ReO4-and AuI2-salts show metal-to-insulator (MI) transition at 126 and 11 K, respectively. Single-crystal X-ray structure analysis of (TMTTP)2X(X=PF6,AsF6,BF4, and ReO4) and (TMTTP)3AuI2reveals that the donor packing motif is categorized as the so-called beta-type. The tight-binding band calculations of (TMTTP)2X (X = ReO4,BF4,PF6, and AsF6) suggest these salts are characterized by quasi-one-dimensional Fermi surfaces. The band calculation based on X-ray structure analysis of (TMTTP)2ReO4at 100 K demonstrates that the MI transition of this salt is associated with the charge ordering with the zigzag stripe pattern.
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