tetrathiafulvalene-4-carboxylic acid | 63822-38-8

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物 - 无环羧酸
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯基硫酯
• 英文名称: tetrathiafulvalene-4-carboxylic acid
• 英文别名: 4-carboxytetrathiafulvalene；1,3-Dithiole-4-carboxylic acid, 2-(1,3-dithiol-2-ylidene)-；2-(1,3-dithiol-2-ylidene)-1,3-dithiole-4-carboxylic acid
• CAS: 63822-38-8
• 化学式: C₇H₄O₂S₄
• 分子量: 248.372
• InChiKey: UWEMSSWRJJCTJK-UHFFFAOYSA-N

物化性质

• 熔点：
  182-184 °C (decomp)
• 沸点：
  318.5±42.0 °C(Predicted)
• 密度：
  1.838±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  139
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tetrathiafulvalene-4-carboxylic acid 在 吡啶 、 4-二甲氨基吡啶 、 三聚氟氰 作用下， 以 二氯甲烷 为溶剂， 反应 13.5h， 生成 2-(ethoxycarbonyl)tetrathiafulvalene
  参考文献：
  名称：

  Fluorocarbonyltetrathiafulvalene: an effective building block for the production of tetrathiafulvalene esters and amides

  摘要：

  4-Fluorocarbonyltetrathiafulvalene has been synthesised under mild conditions, and has been reacted with alcohols and amides to furnish esters and amides in near quantitative yield. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01804-3
• 作为产物：
  描述：

  2-(ethoxycarbonyl)tetrathiafulvalene 在 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 tetrathiafulvalene-4-carboxylic acid
  参考文献：
  名称：

  Creation of a Mixed-Valence State from One-Dimensionally Aligned TTF Utilizing the Self-Assembling Nature of a Low Molecular-Weight Gel

  摘要：

  One-dimensional TTF assemblies have been obtained through the design of low molecular-weight gels, which show a characteristic absorption band at around 1750 nm upon I2 doping, assignable to a mixed-valence state of the TTF assemblies.

  DOI：

  10.1021/ja0552038

文献信息

• Self-assembly of luminescent ternary complexes between seven-coordinate lanthanide(iii) complexes and chromophore bearing carboxylates and phosphonates
  作者：Simon J. A. Pope、Benjamin P. Burton-Pye、Rory Berridge、Tahir Khan、Peter J. Skabara、Stephen Faulkner

  DOI：10.1039/b600598e

  日期：——

  Luminescent lanthanide complexes have been prepared by exploiting the interaction between lanthanide DO3A complexes and chromophore bearing carboxylates or phosphonates. This interaction can be utilised to probe the choice of sensitising chromophore suited to a given lanthanide. Furthermore, ternary complexes obtained from chromophore appended carboxylates dissociate in the presence of phosphate, while those obtained from phosphonates do not.

  通过利用镧系DO3A配合物与含有羧酸盐或膦酸盐的生色团之间的相互作用，制备了发光镧系配合物。这一相互作用可以用于探寻适合特定镧系的敏化生色团的选择。此外，通过连接在羧酸上的生色团获得的二元配合物在存在磷酸盐的情况下会发生解离，而通过连接在膦酸上的生色团获得的配合物则不会。
• Electroactive Supramolecular Self-Assembled Fibers Comprised of Doped Tetrathiafulvalene-Based Gelators
  作者：Tetsu Kitamura、Suguru Nakaso、Norihiro Mizoshita、Yusuke Tochigi、Takeshi Shimomura、Masaya Moriyama、Kohzo Ito、Takashi Kato

  DOI：10.1021/ja053496z

  日期：2005.10.1

  of the derivatives of tetrathiafulvalene (TTF) in liquid crystals. These derivatives are designed and prepared by introducing the TTF moiety to the scaffold derived from amino acids such as L-isoleucine whose derivatives function as organogelators. These TTF-based gelators form stable fibrous aggregates in liquid crystals. These fibers are the first example of hydrogen-bonded one-dimensional aggregates

  通过四硫富瓦烯 (TTF) 衍生物在液晶中的自组装形成了新的电活性超分子纤维。这些衍生物的设计和制备是通过将 TTF 部分引入衍生自氨基酸（如 L-异亮氨酸）的支架中，其衍生物起到有机凝胶剂的作用。这些基于 TTF 的凝胶剂在液晶中形成稳定的纤维聚集体。这些纤维是具有电活性部分的氢键一维聚集体的第一个例子，其电导率是在掺杂后测量的。它们的电子状态也已通过光谱方法表征。单向排列的纤维在经过摩擦的聚酰亚胺表面上的取向液晶溶剂中形成，用于纤维的进一步功能化。
• Improved Syntheses of Carboxytetrathiafulvalene, Formyltetrathiafulvalene and (Hydroxymethyl)tetrathiafulvalene¹: Versatile Building Blocks for New Functionalised Tetrathiafulvalene Derivatives
  作者：Javier Garín、Jesús Orduna、Santiago Uriel、Adrian J. Moore、Martin R. Bryce、Stefan Wegener、Dimitri S. Yufit、Judith A. K. Howard

  DOI：10.1055/s-1994-25510

  日期：——

  Reproducible, high-yielding synthesis of the title compounds 2-4, which are important precursors of highly functionalised tetrathiafulvalene derivatives and multistage redox assemblies, are described. This is demonstrated by the subsequent reactions of 3 and 4 to prepare compounds 9-16; the single crystal X-ray structure of TTF derivative 15 is described.

  描述了标题化合物2-4的可重复、高产率合成，这些化合物是高度功能化的四硫杂双烯衍生物和多级氧化还原组装的重要前体。通过化合物3和4的后续反应来制备化合物9-16，另外还描述了TTF衍生物15的单晶X射线结构。
• Synthesis of amphiphilic, mono-functionalised tetrathiafulvalenes; X-ray crystal structure of 4-(6-sromohexanoyl)tetrathiafulvalene
  作者：Martin R. Bryce、Graeme Cooke、Ajaib S. Dhindsa、Dominique Lorcy、Adrian J. Moore、Michael C. Petty、Michael B. Hursthouse、A. I. Karaulov

  DOI：10.1039/c39900000816

  日期：——

  Reaction of monolithiated-tetrathiafulvalene (TTF) has been used in the synthesis of amphiphilic TTF derivatives bearing long chains attached through carbon, silicon, sulphur, selenium, and tellurium atoms; the single crystal X-ray structure of the title compound is described.

  单片化四硫富瓦烯（TTF）的反应已用于合成带有通过碳，硅，硫，硒和碲原子连接的长链的两亲性TTF衍生物。描述了标题化合物的单晶X射线结构。
• Synthesis and intramolecular charge-transfer properties of new tetrathiafulvalene–σ-tetracyanoanthraquinodimethane diad (TTF–σ-TCNAQ) and triad (TTF–σ-TCNAQ–σ-TTF) molecules
  作者：Pilar de Miguel、Martin R. Bryce、Leonid M. Goldenberg、Andrew Beeby、Vladimir Khodorkovsky、Lev Shapiro、Angelika Niemz、Alej,ro O. Cuello、Vincent Rotello

  DOI：10.1039/a704013j

  日期：——

  We report the use of functionalised electron acceptor tetracyanoanthraquinodimethane (TCNAQ) units in the synthesis of novel diad D–σ-A compounds 6 and 7 [D=tetrathiafulvalenyl (TTF) and ferrocenyl] and the triad TTF–σ-TCNAQ–σ-TTF assembly 8. Compounds 6–8 display a very weak, broad, low-energy intramolecular charge-transfer band in the UV–VIS spectra. Nanosecond laser flash photolysis of compound 6 did not lead to any new transient absorptions in the 300–800 nm region, suggesting that if a charge-separated species is formed upon excitation, then back electron transfer occurs very rapidly to regenerate the ground state. Cyclic voltammetry of compounds 6–8 shows that reversible oxidation processes occur for the TTF and ferrocene moieties, and a reversible two-electron reduction occurs for the TCNAQ moiety. Spectroelectrochemical studies on compound 6 have enabled the redox processes to be assigned to the sequential formation of the TTF radical cation and dication upon oxidation, and the TCNAQ dianion upon reduction. Simultaneous electrochemistry and EPR (SEEPR) experiments provide further evidence for intramolecular interaction between the TTF and TCNAQ moieties in compound 6. Quantum mechanical calculations on compound 6, performed by the AM1 method, predict that in its minimum energy conformation the TTF and TCNAQ moieties are approximately orthogonal to one another, with the TCNAQ unit folded into a butterfly conformation.

  我们报告了利用官能化电子受体四氰基蒽醌二甲烷（TCNAQ）单元合成新型二元 DâÏ-A 化合物 6 和 7 [D=tetrathiafulvalenyl (TTF) and ferrocenyl] 以及三元 TTFâÏ-TCNAQâÏ-TTF 组合物 8 的情况。化合物 6â8 在紫外可见光谱中显示出非常微弱、宽广、低能的分子内电荷转移带。化合物 6 的纳秒激光闪烁光解并没有在 300â800 nm 区域产生任何新的瞬态吸收，这表明如果在激发时形成了电荷分离的物种，那么回电子转移就会非常迅速地发生，从而重新生成基态。化合物 6â8 的循环伏安法显示，TTF 和二茂铁分子发生了可逆的氧化过程，TCNAQ 分子发生了可逆的双电子还原。通过对化合物 6 的光谱电化学研究，可以确定氧化还原过程是 TTF 自由基阳离子和二阳离子在氧化时依次形成，TCNAQ 二阴离子在还原时依次形成。同时进行的电化学和 EPR（SEEPR）实验进一步证明了化合物 6 中 TTF 和 TCNAQ 分子之间的分子内相互作用。通过 AM1 方法对化合物 6 进行的量子力学计算预测，在其最小能量构象中，TTF 和 TCNAQ 分子近似相互正交，TCNAQ 单元折叠成蝶形构象。