Syntheses and Properties of Tetrathiotetrathiafulvalene Derivatives of Cyclophane-Type Structures
| Project/Area Number |
07640706
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | IBARAKI UNIVERSITY |
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Principal Investigator |
KAWADA Yuzo Ibaraki University, Department of Chemistry, Professor, 理学部, 教授 (10152969)
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| Project Period (FY) |
1995 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1995: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | Twin Donor / BEDT-TTF / Charge Transfer Complex / radical ion salt / cyclophane / conductivity / magnetic susceptibility / テトラチアフルバレン誘導体 / 磁性 / テトラチアフルバレン / テトラチオテトラチアフルバレン / 高歪み化合物 / X線構造解析 / 酸化還元電位 / 環化反応 |
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| Research Abstract |
TTF derivatives having cyclophane structure have been proposed to realize new unique arrangements and intermolecular interactions of TTF units. Among them cross-cyclophane twin donors, in which long axs of TTF units are fixed in a cross orientation by four ethylendithio (1), trimethylenedithio (2), and trimethylenediseleno (3) chains, were successfully prepared. Intramolecular double couplings of macrocyclic dmit tetramers to give the central double bond of TTF units are most effective to obtain 1 and 2, whereas 3 was prepared starting from TTF.
Although the donor ability of 1 was low due to a heavy bending of the donor units, that of 2 was the same as BEDT-TTF.The crystal structures of a charge transfer complex, 2・TCNQ,and an ion radical salt 2・Br (1,1,2-TCE) _2, revealed that 2 has an ability to construct characteristic self-assembled structures, recognizing a size and a shape of acceptors or counter ions.
The almost isotropic conducting properties of the ion radical salt was interpreted based on the unique molecular structure of 2.The temperature dependence of the magnetic susceptibility of the salt revealed a basically paramagnetic nature of magnetic behavior, but it showed ferromagnetic interaction at lower temperatures.
In spite of various attempts, twin donors, where long axs of TTF units are held parallel by four ethylendithio or trimethylendithio groups, are yet to be prepared. Conformation and /or orientation of the two TTF units arranged in a parallel fashion compared to cross or extended ones could be the reason.
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Report
(3 results)
Research Products
(9 results)
