4,5-bis(butylthio)tetrathiafulvalene

• 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-bis(butylthio)tetrathiafulvalene
• 英文别名: 4,5-bis(butylthio)-2,2'-bi(1,3-dithiolylidene)；4,5-Bis(butylsulfanyl)-2-(1,3-dithiol-2-ylidene)-1,3-dithiole；4,5-bis(butylsulfanyl)-2-(1,3-dithiol-2-ylidene)-1,3-dithiole
• 化学式: C₁₄H₂₀S₆
• 分子量: 380.709
• InChiKey: CQVQMNWHQUJBIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  152
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,5-bis(butylthio)tetrathiafulvalene 在 正丁基锂 作用下， 以89%的产率得到4',5'-bis(butylthio)-4-iodotetrathiafulvalene
  参考文献：
  名称：

  Self-Assembly of Radially π-Extended Tetrathiafulvalene Tetramers for Visible and Near Infrared Electrochromic Nanofiber

  摘要：

  研究了锚定在 1,2,4,5- 四炔基苯上的径向 π 延伸的四噻吩富戊二烯（TTF）四元分子的自组装和电致变色纳米纤维的形成。带有 SBu 取代基的四聚体在溶液中进行了自组装。通过与 Fe(ClO4)3 化学氧化得到的阳离子四聚体在溶液中表现出明显的电致色性。它们的电子光谱显示了与分子间混合价聚集（TTF//TTF）-+ 和π聚集（TTF-+//TTF-+）相对应的吸收带，这是由于阳离子物种中的分子关联性很强。此外，四聚体还从 CHCl3-hexane 中形成了缠结的纳米级纤维材料。纳米纤维在氧化铟锡电极上的电化学氧化显示了可重复的氧化还原曲线。纳米纤维显示出显著的电致变色行为：纤维的颜色从紫色（中性）变为棕/棕绿色（二阳离子和三阳离子）和绿色（四阳离子）。纳米纤维的这些颜色变化与溶液中的颜色变化相似，氧化纳米纤维的电子能谱反映了阳离子纳米纤维中堆叠的 TTF 单元。

  DOI：

  10.1246/bcsj.20190283
• 作为产物：
  描述：

  4,5-bis(butylthio)-1,3-dithiole-2-thione 在 lithium hydroxide monohydrate 、 亚磷酸三乙酯 作用下， 以 N-甲基吡咯烷酮 为溶剂， 生成 4,5-bis(butylthio)tetrathiafulvalene
  参考文献：
  名称：

  Self-Assembly of Radially π-Extended Tetrathiafulvalene Tetramers for Visible and Near Infrared Electrochromic Nanofiber

  摘要：

  研究了锚定在 1,2,4,5- 四炔基苯上的径向 π 延伸的四噻吩富戊二烯（TTF）四元分子的自组装和电致变色纳米纤维的形成。带有 SBu 取代基的四聚体在溶液中进行了自组装。通过与 Fe(ClO4)3 化学氧化得到的阳离子四聚体在溶液中表现出明显的电致色性。它们的电子光谱显示了与分子间混合价聚集（TTF//TTF）-+ 和π聚集（TTF-+//TTF-+）相对应的吸收带，这是由于阳离子物种中的分子关联性很强。此外，四聚体还从 CHCl3-hexane 中形成了缠结的纳米级纤维材料。纳米纤维在氧化铟锡电极上的电化学氧化显示了可重复的氧化还原曲线。纳米纤维显示出显著的电致变色行为：纤维的颜色从紫色（中性）变为棕/棕绿色（二阳离子和三阳离子）和绿色（四阳离子）。纳米纤维的这些颜色变化与溶液中的颜色变化相似，氧化纳米纤维的电子能谱反映了阳离子纳米纤维中堆叠的 TTF 单元。

  DOI：

  10.1246/bcsj.20190283

文献信息

• Metal cation binding to acetylenic tetrathiafulvalene–pyridine conjugates: affinity tuned by preorganization and cavity size
  作者：Søren Lindbæk Broman、Cecilie Lindholm Andersen、Martyn Jevric、Christian Gregers Tortzen、Ole Hammerich、Mogens Brøndsted Nielsen

  DOI：10.1016/j.tet.2016.08.001

  日期：2016.9

  A series of three structurally related mono-, bidentate and macrocyclic TTF-pyridine hosts were prepared and titrated with several metal cations including Ag+ and Pb2+ and studied using NMR- and UV-vis spectroscopy and cyclic voltammetry. For Ag+, we found an eightfold increase in binding affinity between the bidentate and macrocyclic host and conversely, for Pb2+, a 100-fold drop. Density functional theory (DFT) calculations support the increased binding affinity for Ag+ is due to an N...N distance for the uncomplexed macrocycle very much suited for binding of Ag+ but being too small for Pb2+. The bidentate host, on the other hand, is of a suitable size for Pb2+. (C) 2016 Elsevier Ltd. All rights reserved.
• Synthesis and Electrochromic Properties of Bis(2-tetrathiafulvalenylethynylphenyl)ethynes
  作者：Masahiko Iyoda、Masashi Hasegawa、Yusuke Kobayashi、Kenji Hara、Hideo Enozawa

  DOI：10.3987/com-08-s(f)106

  日期：——

  Bis(2-tetrathiafulvalenylethynylphenyl)ethynes 1a and 1b have been synthesized by the Sonogashira coupling reaction of 4-iodotetrathiafulvalenes with bis(2-ethynylphenyl)ethyne. The dimeric TTFs 1a and 1b form an open-chain anti conformation in the neutral and tetracation states, whereas la and 1b form a helical syn conformation in the mono- and dication states owing to their face-to-face interaction between the two TTF units. Such conformational changes lead to unique electrochromic and on-off switching properties of 1a and 1b in UV-vis-NIR spectra.
• 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.
• Hexagonally Ordered Nanostructures Comprised of a Flexible Disk-like Molecule with High Self-Assembling Properties at Neutral and Cationic States
  作者：Masashi Hasegawa、Hideo Enozawa、Youhei Kawabata、Masahiko Iyoda

  DOI：10.1021/ja069025+

  日期：2007.3.1

  A novel amphiphilic TTF hexamer 1 with a flexible disk-like structure and strong self-aggregation properties has been synthesized. Nanowires fabricated from both 1 and its cation radical 1(.+) in CHCl3/hexane solutions have a hexagonal columnar structure. In contrast, drop-cast films of 1 and 1(.+) exhibit an edge-to-edge close-packed arrangement stacking vertical to the drop-cast surface, indicating stronger dictating effect of surface area for the nanostructure fabrication. The electric conductivity of the wire of1(.+) is 2 orders of magnitude higher than that of the film of 1(.+), reflecting the nostructured, one-dimensional morphology.
• Self-Assembly of Radially π-Extended Tetrathiafulvalene Tetramers for Visible and Near Infrared Electrochromic Nanofiber
  作者：Masashi Hasegawa、Masahiko Iyoda

  DOI：10.1246/bcsj.20190283

  日期：2020.1.15

  The self-assembly and electrochromic nanofiber formation of radially π-extended tetrathiafulvalene (TTF) tetramers anchored to 1,2,4,5-tetraethynylbenzene were investigated. The tetramer with SBu-substituents underwent self-assembly in solution. Cationic species of the tetramer, obtained by chemical oxidation with Fe(ClO4)3, exhibited a marked electrochromism in the solution. Their electronic spectra revealed absorption bands corresponding to intermolecular mixed-valence aggregation based on (TTF//TTF)•+, and π-aggregation based on (TTF•+//TTF•+) due to the strong molecular association in the cationic species. Furthermore, the tetramer formed an entangled nanoscale fibrous material from CHCl3–hexane. Electrochemical oxidation of the nanofiber on an indium tin oxide electrode revealed a repeatable redox profile. The nanofiber displayed remarkable electrochromic behavior: the color of the fiber changed from purple (neutral) to brown/brownish green (dication and trication) and green (tetracation). These color changes of the nanofiber are similar to those in solution, and the electronic spectra of the oxidized nanofibers reflected the stacked TTF units in the cationic nanofibers.

  研究了锚定在 1,2,4,5- 四炔基苯上的径向 π 延伸的四噻吩富戊二烯（TTF）四元分子的自组装和电致变色纳米纤维的形成。带有 SBu 取代基的四聚体在溶液中进行了自组装。通过与 Fe(ClO4)3 化学氧化得到的阳离子四聚体在溶液中表现出明显的电致色性。它们的电子光谱显示了与分子间混合价聚集（TTF//TTF）-+ 和π聚集（TTF-+//TTF-+）相对应的吸收带，这是由于阳离子物种中的分子关联性很强。此外，四聚体还从 CHCl3-hexane 中形成了缠结的纳米级纤维材料。纳米纤维在氧化铟锡电极上的电化学氧化显示了可重复的氧化还原曲线。纳米纤维显示出显著的电致变色行为：纤维的颜色从紫色（中性）变为棕/棕绿色（二阳离子和三阳离子）和绿色（四阳离子）。纳米纤维的这些颜色变化与溶液中的颜色变化相似，氧化纳米纤维的电子能谱反映了阳离子纳米纤维中堆叠的 TTF 单元。