4,5,4''',5'''-tetrakis(methylsulfanyl)-4',4''-bitetrathiafulvalene | 111082-53-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫醇
• 英文名称: 4,5,4''',5'''-tetrakis(methylsulfanyl)-4',4''-bitetrathiafulvalene
• 英文别名: 4,5,4''',5'''-tetrakis(methylthio)-4',4''-bitetrathiafulvalene；2-[4-[2-[4,5-Bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-1,3-dithiol-4-yl]-1,3-dithiol-2-ylidene]-4,5-bis(methylsulfanyl)-1,3-dithiole
• CAS: 111082-53-2
• 化学式: C₁₆H₁₄S₁₂
• 分子量: 591.079
• InChiKey: MTJDHBWWBBJGBK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  304
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  二甲基二硫 、 4,5,4''',5'''-tetrakis(methylsulfanyl)-4',4''-bitetrathiafulvalene 在 lithium diisopropyl amide 作用下， 以40%的产率得到4,5,5',5'',4''',5'''-hexakis(methylsulfanyl)-4',4''-bitetrathiafulvalene
  参考文献：
  名称：

  Helical Tetrathiafulvalene Oligomers. Synthesis and Properties of Bi-, Ter-, and Quatertetrathiafulvalenes

  摘要：

  [GRAPHICS]A series of fully methylthiolated bi-, ter-, and quatertetrathiafulvalenes have been synthesized using cross- and homocoupling reactions of tetrathiafulvalenylzinc derivatives; the tetracation-tetraradical derived from the helical tetrathiafulvalene tetramer exhibits an intramolecular association of the terminal cation-radicals.

  DOI：

  10.1021/ol0000915
• 作为产物：
  描述：

  2,3-bis(methylthio)tetrathiafulvalene 在 正丁基锂 、 magnesium bromide 、 iron(III) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以51%的产率得到4,5,4''',5'''-tetrakis(methylsulfanyl)-4',4''-bitetrathiafulvalene
  参考文献：
  名称：

  Synthesis of bitetrathiafulvalenes with FeCl3-mediated homo-coupling of tetrathiafulvalenylmagnesium bromide and formation of nanostructures from bitetrathiafulvalenes having long alkylthio chains

  摘要：

  The FeCl3-mediated homo-coupling of 4,5-bis(alkylthio)-4'-tetrathiafulvalenylmagnesium bromide 5 produced the corresponding bitetrathiafulvalene derivatives 2a-d in moderate yields (25-51%). Bitetrathiafulvalenes 2c and 2d having long alkylthio chains formed nanostructures and showed bulk electric conductivities (sigma(rt) = 2.6 - 8.0 x 10(-5) S cm(-1)) in the neutral state owing to the fastener effect. Interestingly, the nanofiber of tetrakis(dodecylthio)bitetrathiafulvalene 2d exhibited a p-type semiconductivity as detected by AFM. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.11.106

文献信息

• New bi(tetrathiafulvalenyl) derivatives and their radical cations: synthetic and X-ray structural studies
  作者：Derek E. John、Adrian J. Moore、Martin R. Bryce、Andrei S. Batsanov、Michael A. Leech、Judith A. K. Howard

  DOI：10.1039/b000790k

  日期：——

  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.

  一系列双（四硫富瓦烯基）衍生物已通过Ullmann偶联反应（在回流的N,N-二甲基甲酰胺中使用铜）或通过在20°C下与铜（I）噻吩-2-羧酸盐（CuTC）在1-甲基吡咯烷-2-酮中反应，从碘代TTF前体制备得到。溶液电化学和UV-VIS光谱学研究表明，在这些体系中，两个TTF单元之间没有显著的键间相互作用。报道了4,5,5',5'',4''',5'''-六甲硫基-4',4''-双四硫富瓦烯9和4,5:4''',5'''-双（乙二硫基）-5',5''-二甲基-4',4''-双四硫富瓦烯8+··ClO4−的1∶1高氯酸盐半导体的X射线晶体结构。在9中，中心键的扭转角度为89°，在8+··ClO4−中为77°。8+··ClO4−的晶体堆积特征为通过硫原子接触的阳离子形成的褶皱层，平行于（001）平面；阴离子位于平行于z轴并穿过阳离子图案的无穷通道中。
• Redox-active proligands from the direct connection of 1,3-dithiol-2-one to tetrathiafulvalene (TTF): syntheses, characterizations and metal complexation
  作者：Franck Camerel、Olivier Jeannin、Gilles Yzambart、Bruno Fabre、Dominique Lorcy、Marc Fourmigué

  DOI：10.1039/c3nj41097h

  日期：——

  In the search for novel tetrathiafulvalene-substituted dithiolene ligands, two tetrathiafulvalene (TTF) molecules directly connected to 1,3-dithiol-2-one fragments have been synthesized and characterized by single crystal X-ray diffraction, electrochemical and spectroscopic analyses. TTF1 was obtained, in moderate yield, by the cross-coupling of 4,5-bis(methylthio)-1,3-dithiole-2-one with 4,4′-bis(1,3-dithiole-2-one) in triethylphosphite, whereas for TTF2, the 1,3-dithiol-2-one fragment was introduced, in high yield, by an original reaction of the alkyne group of an ethynyl TTF (Me3TTF–CCH) with xanthogen in the presence of a radical initiator. Opening of the 1,3-dithiol-2-one fragments with sodium methanolate leads to the formation of two new 1,2-dithiolate ligands functionalized with redox-active TTF moieties, which can efficiently coordinate metals. As an illustration, two original heteroleptic bis(cyclopentadienyl)dithiolene titanium complexes were isolated and characterized.

  在寻找新型四硫富瓦烯取代二硫烯配体的过程中，我们合成了两种直接连接四硫富瓦烯（TTF）分子与1,3-二硫杂环戊烯-2-酮片段的化合物，并通过单晶X射线衍射、电化学和光谱分析进行了表征。TTF1是通过4,5-双(甲硫基)-1,3-二硫杂环戊烯-2-酮与4,4′-双(1,3-二硫杂环戊烯-2-酮)在三乙基亚磷酸酯中的交叉偶联反应制备的，产率中等；而TTF2则是通过一种原始的反应，在自由基引发剂存在下，将乙炔基TTF（Me3TTF–CCH）的炔基与黄原酸酯反应引入1,3-二硫杂环戊烯-2-酮片段，产率较高。用甲醇钠打开1,3-二硫杂环戊烯-2-酮片段，形成了两种新的含氧化还原活性TTF基团的1,2-二硫醇配体，这些配体能够有效地与金属配位。作为示例，我们分离并表征了两种新颖的杂配体双(环戊二烯基)二硫烯钛配合物。
• Helical Tetrathiafulvalene Oligomers. Synthesis and Properties of Bi-, Ter-, and Quatertetrathiafulvalenes
  作者：Masahiko Iyoda、Kenji Hara、Yoshiyuki Kuwatani、Shigeru Nagase

  DOI：10.1021/ol0000915

  日期：2000.7.1

  [GRAPHICS]A series of fully methylthiolated bi-, ter-, and quatertetrathiafulvalenes have been synthesized using cross- and homocoupling reactions of tetrathiafulvalenylzinc derivatives; the tetracation-tetraradical derived from the helical tetrathiafulvalene tetramer exhibits an intramolecular association of the terminal cation-radicals.
• Synthesis of bitetrathiafulvalenes with FeCl3-mediated homo-coupling of tetrathiafulvalenylmagnesium bromide and formation of nanostructures from bitetrathiafulvalenes having long alkylthio chains
  作者：Yohei Honna、Eigo Isomura、Hideo Enozawa、Masashi Hasegawa、Masayoshi Takase、Tohru Nishinaga、Masahiko Iyoda

  DOI：10.1016/j.tetlet.2009.11.106

  日期：2010.1

  The FeCl3-mediated homo-coupling of 4,5-bis(alkylthio)-4'-tetrathiafulvalenylmagnesium bromide 5 produced the corresponding bitetrathiafulvalene derivatives 2a-d in moderate yields (25-51%). Bitetrathiafulvalenes 2c and 2d having long alkylthio chains formed nanostructures and showed bulk electric conductivities (sigma(rt) = 2.6 - 8.0 x 10(-5) S cm(-1)) in the neutral state owing to the fastener effect. Interestingly, the nanofiber of tetrakis(dodecylthio)bitetrathiafulvalene 2d exhibited a p-type semiconductivity as detected by AFM. (C) 2009 Elsevier Ltd. All rights reserved.