New bi(tetrathiafulvalenyl) derivatives and their radical cations: synthetic and X-ray structural studies
New bi(tetrathiafulvalenyl) derivatives and their radical cations: synthetic and X-ray structural studies
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新型双（四硫富瓦烯基）衍生物及其自由基阳离子：合成和 X 射线结构研究
DOI：
10.1039/b000790k
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发表时间：
2000
影响因子：
--
通讯作者：
J. Howard
中科院分区：
文献类型：
--
作者：
D. E. John;A. Moore;M. Bryce;A. Batsanov;M. Leech;J. Howard
通过乌尔曼偶联（铜在N，N-二甲基甲酰胺中回流）或与铜(I)噻吩-2-羧酸（CuTC）在1-甲基吡咯烷-2- 1中在20℃下反应，以碘- ttf前体为原料制备了一系列双（四硫代戊烯基）衍生物。溶液电化学和紫外-可见光谱研究表明，在这些体系中，两个TTF单元之间没有明显的通键相互作用。报道了4,5,5 ',5 ',4 ',5 ' ' -六基斯（甲基磺酰基）-4 ',4 ' -双四硫代基)-5 ',5 ' -二甲基-4 ',4 ' -双四硫代基- 8+··ClO4 -的1∶1高氯酸盐和4,5,5 ',5 ' -二甲基-4 ',4 ' -双四硫代基- 9 +的x射线晶体结构。在9和8+··ClO4−中，围绕中心键的扭转角分别为89°和77°。8+··ClO4−的晶体填充特征为平行于（001）平面的褶皱层，阳离子通过其硫原子接触；阴离子占据无限通道，平行于z轴并穿过阳离子基序。
A series of bi(tetrathiafulvalenyl) derivatives has been prepared from iodo-TTF precursors by Ullmann coupling (copper in refluxing N,N-dimethylformamide) or by reaction with copper(I) thiophene-2-carboxylate (CuTC) in 1-methylpyrrolidin-2-one at 20 °C. Solution electrochemical and UV-VIS spectroscopic studies suggest that there is no significant through-bond interaction between the two TTF units in these systems. The X-ray crystal structures are reported for 4,5,5′,5′′,4′′′,5′′′-hexakis(methylsulfanyl)-4′,4′′-bitetrathiafulvalene 9 and a semiconducting 1∶1 perchlorate salt of 4,5:4′′′,5′′′-bis(ethylenedithio)-5′,5′′-dimethyl-4′,4′′-bitetrathiafulvalene 8+··ClO4−. The torsion angle around the central bond is 89° in 9 and 77° in 8+··ClO4−. The crystal packing of 8+··ClO4− is characterised by puckered layers, parallel to the (001) plane, of cations contacting via their sulfur atoms; the anions occupy infinite channels, parallel to the z-axis and running through the cation motif.