Alternative synthesis of (Z),(Z)-4,5;4′,5′-bis(1,4-dioxanediyl-2,3-dithio)tetrathiafulvalene (cis,cis-BDDT–TTF), and the preparation, EPR properties and structure of the radical cation salt (cis,cis-BDDT–TTF)2I3
Alternative synthesis of (Z),(Z)-4,5;4′,5′-bis(1,4-dioxanediyl-2,3-dithio)tetrathiafulvalene (cis,cis-BDDT–TTF), and the preparation, EPR properties and structure of the radical cation salt (cis,cis-BDDT–TTF)2I3
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(Z),(Z)-4,5;4,5-双(1,4-二恶烷二基-2,3-二硫基)四硫富瓦烯(cis,cis-BDDT–TTF)的替代合成及其制备，自由基阳离子盐 (cis,cis-BDDT–TTF)2I3 的 EPR 性质和结构
DOI：
10.1039/jm9950501647
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发表时间：
1995
影响因子：
--
通讯作者：
C. Campana
中科院分区：
文献类型：
--
作者：
A. Kini;U. Geiser;Hsien‐Hau Wang;K. Lykke;Jack M. Williams;C. Campana
提出了一种通过顺式-β 1合成标题化合物（BEDT-TTF或ET的衍生物）的替代方法，该方法是在（E）-2，3-二氯-1，4-二氧六环和双（4，5-二巯基-1，3-二硫杂环戊烯-2-基）锌酸盐之间的反应中试图制备反式异构体时意外地获得的。自由基阳离子盐（cis，cis-BDDT-TTF）_2I_3是通过电化学方法制备的，其结构由X射线衍射确定，由供体分子的柱状堆积和柱间的三碘负离子组成.这种结构明显不同于基于ET和相关电子供体分子的有机导体和超导体的层状结构，供体层与阴离子层交替。发现该盐表现出大的EPR线宽（130 G，g= 2.0045），这比在其他有机导体和超导体中发现的大得多。大的EPR线宽可能是三维（3D）电子离域的反映，盐的柱状结构的结果。
An alternative synthesis of the title compound (a derivative of BEDT–TTF or ET)via the cis-thione 1, which was unexpectedly obtained while attempting to prepare the trans isomer in the reaction between (E)-2,3-dichloro-1,4-dioxane and bis(4,5-dimercapto-1,3-dithiole-2-thione)zincate, is presented. The radical cation salt (cis,cis-BDDT–TTF)2I3 was prepared by electrochemical methods, and its structure, as determined by X-ray diffraction, consists of a columnar packing of the donor molecules with the triiodide anions residing between the columns. This structure is distinctly different from the layered structure, donor layers alternating with anion layers, of organic conductors and superconductors based on ET and related electron-donor molecules. The salt was found to exhibit a large EPR linewidth (130 G, g= 2.0045), which is much larger than those found in other organic conductors and superconductors. The large EPR linewidth may be a reflection of the three-dimensional (3D) electron delocalization, a consequence of the columnar structure of the salt.