Organic Molecular Conductors Based on Tetramethyl-TTP: Structural and Electrical Properties Modulated by the Anion Size and Shape
Organic Molecular Conductors Based on Tetramethyl-TTP: Structural and Electrical Properties Modulated by the Anion Size and Shape
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基于四甲基-TTP的有机分子导体：阴离子尺寸和形状调节的结构和电性能
DOI：
10.1021/acs.inorgchem.1c04004
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发表时间：
2022
影响因子：
4.6
通讯作者：
Misaki Yohji
中科院分区：
文献类型：
--
作者：
Shirahata Takashi;Kohno Shuhei;Furuta Keisuke;Katayama Shogo;Suzuki Kento;Kawamoto Tadashi;Mori Takehiko;Misaki Yohji
合成了双稠合四硫富瓦烯的四甲基衍生物2，5-双（4，5-二甲基-1，3-二硫代-2-亚基）-1，3，4，6-四硫代戊二烯（TMTTP）。由TMTTP组成的自由基阳离子盐大多具有高的电导率，在单晶上的σrt= 101 - 102 S cm-1。TMTTP导体的阴离子形状和尺寸调节电性能。PF 6-和AsF 6-盐表现出金属导电性低至10 K，而ReO 4-和AuI 2-盐显示金属到绝缘体（MI）的转变，分别在126和11 K。（TMTTP）2X（X = PF 6、AsF 6、BF 4和ReO 4）和（TMTTP）3AuI 2的单晶X射线结构分析表明，其施主堆积模体属于β型。（TMTTP）2X（X = ReO 4，BF 4，PF 6和AsF 6）的紧束缚带计算表明，这些盐具有准一维的费米面.基于100 K下（TMTTP）2 ReO 4的X射线结构分析的能带计算表明，该盐的MI跃迁与Z字形条纹的电荷有序化有关.
The tetramethyl derivative of bis-fused tetrathiafulvalene, 2,5-bis(4,5-dimethyl-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (TMTTP), has been successfully synthesized. Most of the radical cation salts consisting of TMTTP feature a high electrical conductivity of σrt= 101to 102S cm–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 β-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.