3,4,3',4'-tetrakis(hydroxymethyl)tetrathiafulvalene | 122301-05-7

• 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: 3,4,3',4'-tetrakis(hydroxymethyl)tetrathiafulvalene
• 英文别名: tetrakis(hydroxymethyl)tetrathiafulvalene；[2-[4,5-Bis(hydroxymethyl)-1,3-dithiol-2-ylidene]-5-(hydroxymethyl)-1,3-dithiol-4-yl]methanol
• CAS: 122301-05-7
• 化学式: C₁₀H₁₂O₄S₄
• 分子量: 324.467
• InChiKey: WSIUZKWXRLTWCB-UHFFFAOYSA-N

物化性质

• 沸点：
  540.2±50.0 °C(Predicted)
• 密度：
  1.697±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  182
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3,4,3',4'-tetrakis(hydroxymethyl)tetrathiafulvalene 在 三溴化磷 作用下， 以70%的产率得到tetrakis(bromomethyl)tetrathiafulvalene
  参考文献：
  名称：

  Rigidified tetrathiafulvalene–[60]fullerene assemblies: towards the control of through-space orientation between both electroactive units

  摘要：

  我们最近的研究工作集中在融合的TTF–C60二聚体、(TTF)n–C60多聚体和C60–TTF–C60哑铃三聚体，这些体系中受体C60通过刚性的环己烯环与供体四硫富瓦烯双重连接。此方法的开发旨在控制供体和受体之间的相对方向和距离。因此，由于分子的特殊拓扑结构，空间内的相互作用在光诱导电子及/或能量转移过程中预计将占主导地位。这种加合物中连接的C60和TTF色团不仅相互接近，而且具有最佳的轨道取向，从而促进这些跨空间的电子相互作用。这些新的基于C60的组装体是通过[4 + 2]迪尔斯－阿尔德环加成反应合成的。文中讨论了其合成过程中考虑的不同方法，并描述了它们的分析、光谱特性及电化学性质。选择性电氧化或还原生成了相应的自由基阳离子和自由基阴离子，这些都通过电子顺磁共振（EPR）进行了表征。这些基于C60的组装体也被研究用于其非线性光学和光限制应用。此外，设计为可溶于有机溶剂的融合C60–TTF–C60哑铃三聚体中的分子内光诱导电荷分离和电荷重组过程通过时间分辨吸收和荧光技术进行了研究。在基态中，稳态吸收光谱表明C60基团与TTF基团之间存在显著的相互作用，而荧光光谱则显示在单重激发态中也存在较强的相互作用。纳秒瞬态吸收光谱显示了电荷分离的自由基对C60–TTF˙+–C60˙–，其在苯腈中表征的寿命约为20纳秒。

  DOI：

  10.1039/b201695h
• 作为产物：
  描述：

  2,3,6,7-Tetrakis(acetoxymethyl)tetrathiafulvalene 在 氢氧化钾 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 以92%的产率得到3,4,3',4'-tetrakis(hydroxymethyl)tetrathiafulvalene
  参考文献：
  名称：

  Synthesis and Properties of 2,3,6,7-Tetrakis(alkoxymethyl)tetrathiafulvalenes

  摘要：

  A family of newly prepared tetrakis(alkoxymethyl)-substituted tetrathiafulvalene (TTF) derivatives 1 show melting point behavior typical for increasing length of their flexible alkyl chains and molecular weights. No evidence for the formation of a stable,liquid crystalline mesophase was found. The X-ray crystal structure of 1 (n = 7) shows it to have a flat central core. Its anodic reactivity is entirely parallel to that of tetrathiafulvalene itself. The dark conductivity of a thin film of 1 (n = 7) is sensitive to temperature, with dark conductivity being enhanced at higher temperatures by as much as 5 orders of magnitude from the level observed in previously studied TTFs. Short-circuit photocurrent is observed in a symmetrical ITO sandwich cell containing a thin layer of 1 (n = 7): in such a cell, charge can be separated under bias and maintained for at least 8 h.

  DOI：

  10.1021/jo00101a009

文献信息

• Relative basicities of the oxygen atoms of the Linquist polyoxometalate [Mo6O19]2− and their recognition by hydroxyl groups in radical cation salts based on functionalized tetrathiafulvalene π donors
  作者：Anne Dolbecq、Aude Guirauden、Marc Fourmigué、Kamal Boubekeur、Patrick Batail、Marie-Madeleine Rohmer、Marc Bénard、Claude Coulon、Marc Sallé、Philippe Blanchard

  DOI：10.1039/a809442j

  日期：——

  Electrocrystallization of three hydroxylated donor molecules derived from tetrathiafulvalene (TTF) or ethylenedithiotetrathiafulvalene (EDT-TTF), i.e. Me3TTF-CH2OH, EDT-TTF(CH2OH)2 and TTF(CH2OH)4, in the presence of [n-Bu4N+]2[Mo6O19]2– afforded 2∶1 cation radical salts, [donor+˙]2[Mo6O19]2–, whose crystal structures have been solved by X-ray diffraction. In the three different salts complex hydrogen bond networks develop in the solid state where the oxygen atoms of both the hydroxyl groups and the [Mo6O19]2– anions act as hydrogen bond acceptors. The observed hydrogen bonding directed toward one surface, bridging oxygen atom of [Mo6O19]2– is rationalized by an analysis of ab initio calculations of the distribution of electrostatic potentials.

  在[n-Bu4N+]2[Mo6O19]2â的存在下，从四噻吩富戊二烯（TTF）或亚乙基二硫代四噻吩富戊二烯（EDT-TTF）衍生的三种羟基化供体分子（即Me3TTF-CH2OH、EDT-TTF(CH2OH)2 和 TTF(CH2OH)4，在[n-Bu4N+]2[Mo6O19]2â的存在下生成 2â¶1 阳离子自由基盐[供体+Ë]2[Mo6O19]2â，其晶体结构已通过 X 射线衍射解决。在这三种不同的盐中，羟基和[Mo6O19]2â阴离子的氧原子都是氢键的受体，在固态下形成了复杂的氢键网络。通过对静电位分布的 ab initio 计算分析，可以合理地解释观察到的指向 [Mo6O19]2â 的一个表面桥接氧原子的氢键。
• Tetraformyltetraselenafulvalene (TFTSeF): synthesis and some uses as a precursor of polyfunctionalized tetraselenafulvalenes
  作者：Marc Sallé、Alain Gorgues、Jean-Marc Fabre、Klaus Bechgaard、Michel Jubault、Fernand Texier

  DOI：10.1039/c39890001520

  日期：——

  A short synthesis of tetraformyltetraselenafulvalene (TFTSeF) is presented, and a few preliminary results emphasize its use as an efficient precursor of tetrasubstituted TSeFs such as a tetravinylic derivative, via a Wittig reaction, and tetrakis(hydroxymethyl)–TSeF by a simple NaBH4 reduction.

  介绍了四甲酰基四硒富勒烯（TFTSeF）的简短合成，一些初步结果强调了其通过Wittig反应作为四取代TSeF（如四乙烯基衍生物）和四（羟甲基）-TSeF的有效前体的作用，通过简单的NaBH 4还原。
• Radical cation salts of TTF(CH2OH)4 with cyanide anions: Synthesis, crystal structure and magnetic properties of [TTF(CH2OH)4][TCNQF4] and [TTF(CH2OH)4]3[18-crown-6⊂K][M(CN)6]·DMF (M=Fe, Co)
  作者：Sandrine Perruchas、Kamal Boubekeur、Philippe Molinié

  DOI：10.1016/j.poly.2005.04.010

  日期：2005.8

  anions. In the structures, the organic molecules are combined in electronically isolated and diamagnetic dimers (1) or trimers (2a–b). The structural analysis reveals strong hydrogen bonds between the hydroxyl groups of the organic molecules and also between the latter and the cyano groups of the anions. This study shows that the association of hydrogen bond acceptor anions to hydrogen bond donor functionalized

  [TTF（CH 2 OH）4 ] [TCNQF 4 ]（1）和[TTF（CH 2 OH）4 ] 3 [18-crown-描述了6 = K] [M（CN）6 ]·DMF，其中M = Fe（2a）和M = Co（2b）。这些盐将羟基官能化的有机供体四（羟甲基）四硫富瓦烯（TTF（CH 2 OH）4）与两种不同类型的氰化物阴离子缔合。在结构中，有机分子结合在电子隔离的和抗磁性的二聚体中（1）或三聚体（2a – b）。结构分析揭示了有机分子的羟基之间以及有机分子和阴离子的氰基之间的强氢键。这项研究表明，氢键受体阴离子与氢键供体官能化的TTF的缔合是生产具有原始结构组织的新分子材料的良好策略。
• Tetraformyltetrathiafulvalene (TFTTF) and acetals, precursors of polyfunctionalized TTFs.
  作者：M. Salle、A. Gorgues、M. Jubault、K. Boubekeur、P. Batail

  DOI：10.1016/s0040-4020(01)92250-1

  日期：1992.4

  A short synthesis of 1,3-dithiol-2-thiones bearing two aldehyde functionalities, free and/or masked as diethylacetals is described. They are shown to be convenient precursors for synthesizing di- and tetraformyl-TTF. When submitted to four-fold nucleophilic attacks, the latter readily affords new substituted derivatives such as the bis-(pyridazino)-TTF 8, the tetrakis-(hydroxymethyl)-TTF 9 and the tetravinylic-TTF 10 whose pi-donor ability has been characterized.
• Solid-State Transformations of Zinc 1,4-Benzenedicarboxylates Mediated by Hydrogen-Bond-Forming Molecules
  作者：Mark Edgar、Robert Mitchell、Alexandra M. Z. Slawin、Philip Lightfoot、Paul A. Wright

  DOI：10.1002/1521-3765(20011203)7:23<5168::aid-chem5168>3.0.co;2-s

  日期：2001.12.3

  The zinc 1,4-benzenedicarboxylates [Zn3(bdc)3(H2O)3] . 4 DMF (1; bdc = 1,4-benzenedicarboxylate), [Zn(bdc)(H2O)] . DMF (2), and [Zn(bdc)] DMF (3) crystallise at room temperature from mixtures of toluene/ dimethylformamide (DMF) under concentrated, dilute and dry conditions, respectively. The structure of phase 1 (monoclinic: P2(1)/c, a 13.065(1), b = 9.661(1), c = 18.456(1) A, beta = 106.868(2) degrees) consists of layers containing stacks of three zinc cations linked by mono- and bidentate bdc groups. Structure 1 converts to the known phase 2 by an irreversible, reconstructive phase transformation, whereas 2 and 3 interconvert reversibly upon the loss or addition of water. Removal of all solvent molecules included during crystallisation gives poorly crystalline [Zn(bdc)] (4), which is readily converted to highly crystalline solids upon contact with hydrogen-bond-forming molecules such as water, DMF and small alcohols. The crystal structures of the mono- and dihydrates [Zn(bdc)(H2O)] (6) and [Zn(bdc)-(H2O)2] (7) have been determined ab initio from powder X-ray diffraction data (compound 6, monoclinic: C2/c, a = 17.979(1), b = 6.352(1), c = 7.257(1) A, beta=91.477(1) compound 7, monoclinic: C2/c, a = 14.992(1), b = 5.0303(2), c = 12.098(1) A, beta = 103.82(1) degrees). The methanol adduct [Zn3(bdc)3] . 6CH3OH (5) is the same as that prepared previously by direct crystallisation. Comparison of these adduct structures with those prepared directly reveal that they are formed by in situ recrystallisations. Subsequent removal of included molecules gives amorphous [Zn(bdc)], which can be recrystallised again when placed in contact with hydrogen-bond-forming molecules.