4,5-Bis(hydroxymethyl)-2-(methylthio)-1,3-dithiolium iodide | 159223-13-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 4,5-Bis(hydroxymethyl)-2-(methylthio)-1,3-dithiolium iodide
• 英文别名: 1,3-Dithiol-1-ium, 4,5-bis(hydroxymethyl)-2-(methylthio)-, iodide；[5-(hydroxymethyl)-2-methylsulfanyl-1,3-dithiol-1-ium-4-yl]methanol;iodide
• CAS: 159223-13-9
• 化学式: C₆H₉O₂S₃*I
• 分子量: 336.239
• InChiKey: GJSAXNHBSSBGNK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  122
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4,5-Bis(hydroxymethyl)-2-(methylthio)-1,3-dithiolium iodide 在 吡啶 、 咪唑 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 32.0h， 生成 9-[4,5-bis{(tert-butyl(diphenyl)silyloxy)methyl}-1,3-dithiol-2-ylidene]-9,10-dihydroanthracen-10-one
  参考文献：
  名称：

  在结构上不同的C60 / exTTF集成中探测电荷分离。

  摘要：

  本工作的范围是强调通过不同的C60 / exTTF联结（exTTF = 9,10-双（1,3-二硫醇-2-亚烷基）-9,10-二氢蒽）-通过蒽单元产生的作用或二硫环。特别强调的是光致电子转移特征。因此，我们设计了一系列新的C60-exTTF集成体，它们是通过1,3-偶极环加成反应和Diels-Alder环加成反应合成的，其中exTTF单元通过两个单键（3a-c，4）和一个亚乙烯基与C60分开单元（5a）或两个亚乙烯基单元（5b）。循环伏安法揭示了两性氧化还原行为，在4和5a，5b中三甲基取代的exTTF部分具有显着强的电子给体能力。稳态和时间分辨光解技术表明，在（3a-c，4和5a，b）受到快速电子转移淬灭。通过瞬态吸收光谱法鉴定了所得的电荷分离状态，即C60 *（-）-exTTF * +。我们确定了苄腈中大约200 ns的自由基对寿命。这表明（i）exTTF * +的正电荷在整个供体上是局域化的，而不是在1

  DOI：

  10.1021/jo034432e
• 作为产物：
  描述：

  1,3-二硫杂环戊二烯-2-硫酮-4,5-二甲酸二甲酯 在 sodium tetrahydroborate 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 9.0h， 生成 4,5-Bis(hydroxymethyl)-2-(methylthio)-1,3-dithiolium iodide
  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

• Rigidified tetrathiafulvalene–[60]fullerene assemblies: towards the control of through-space orientation between both electroactive units
  作者：David Kreher、Michel Cariou、Sheng-Gao Liu、Eric Levillain、Jaume Veciana、Concepció Rovira、Alain Gorgues、Piétrick Hudhomme

  DOI：10.1039/b201695h

  日期：2002.6.21

  Our recent works on fused TTF–C60 dyads, (TTF)n–C60 polyads and C60–TTF–C60 dumbbell triads in which the acceptor C60 is doubly tethered to the donor tetrathiafulvalene through a rigidified cyclohexene ring are presented. This approach was developed in order to control the relative orientation as well as the distance between both donor and acceptor entities. Thereby, through-space interactions which are of great importance for photoinduced electron- and/or energy-transfer processes are expected to dominate because of the special topology of the molecules. The two linked C60 and TTF chromophores in such adducts are not only in close proximity but also have optimal orbital orientations, thus facilitating these through-space electronic interactions. These new C60-based assemblies were synthesized by [4 + 2] Diels–Alder cycloaddition reactions. The different methodologies considered for their synthesis are discussed, their analytical, spectroscopic characterizations and electrochemical properties are also described. The selective electro-oxidation or reduction afforded the corresponding radical cation and radical anion which were characterized by EPR. These C60-based assemblies were studied for their nonlinear optical and optical limiting applications. Moreover, intramolecular photoinduced charge-separation and charge-recombination processes in a fused C60–TTF–C60 dumbbell triad which was designed to be soluble in organic solvents were investigated by time-resolved absorption and fluorescence techniques. Appreciable interaction between the C60 moiety and TTF moiety in the ground state was suggested by steady-state absorption spectra and the fluorescence spectra showed considerable interaction in the singlet excited state. The nanosecond transient absorption spectra displayed the formation of the charge-separated radical pair C60–TTF˙+–C60˙−, characterized by a lifetime of ca. 20 ns in benzonitrile.

  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。
• Synthesis of tetrahydroxy-π-extended tetrathiafulvalenes as new supramolecular redox building blocks
  作者：Marta C Dı́az、Beatriz Illescas、Nazario Martı́n

  DOI：10.1016/s0040-4039(02)02779-x

  日期：2003.1

  A novel p-quinonoid π-extended tetrathiafulvalene (exTTF) endowed with four hydroxy groups with different reactivity (phenol and alcohol) has been synthesized as a supramolecular redox building block. The redox properties, studied by cyclic voltammetry, reveal a strong donor ability and, despite the different substitution pattern on the 1,3-dithiole rings, only one oxidation wave involving two electrons

  合成了具有四个不同反应性羟基（酚和醇）的新型对苯二酚π-延伸的四硫富瓦烯（exTTF），作为超分子氧化还原构件。通过循环伏安法研究的氧化还原性质显示出强大的供体能力，尽管在1,3-二硫醇环上具有不同的取代方式，但只有一个氧化波涉及两个电子，形成了指示物质。
• Synthesis and Properties of 2,3,6,7-Tetrakis(alkoxymethyl)tetrathiafulvalenes
  作者：Marye Anne Fox、Horng-long Pan

  DOI：10.1021/jo00101a009

  日期：1994.11

  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.
• Probing Charge Separation in Structurally Different C₆₀/exTTF Ensembles
  作者：Marta C. Díaz、M Angeles Herranz、Beatriz M. Illescas、Nazario Martín、Nicolas Godbert、Martin R. Bryce、Chuping Luo、Angela Swartz、Greg Anderson、Dirk M. Guldi

  DOI：10.1021/jo034432e

  日期：2003.10.1

  The scope of the present work is to highlight the effects stemming from different C60/exTTF linkages (exTTF = 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene)-either via an anthracene unit or a dithiole ring. Particular emphasis is placed on photoinduced electron-transfer features. Therefore, we devised a new series of C60-exTTF ensembles, synthesized via 1,3-dipolar cycloaddition and Diels-Alder

  本工作的范围是强调通过不同的C60 / exTTF联结（exTTF = 9,10-双（1,3-二硫醇-2-亚烷基）-9,10-二氢蒽）-通过蒽单元产生的作用或二硫环。特别强调的是光致电子转移特征。因此，我们设计了一系列新的C60-exTTF集成体，它们是通过1,3-偶极环加成反应和Diels-Alder环加成反应合成的，其中exTTF单元通过两个单键（3a-c，4）和一个亚乙烯基与C60分开单元（5a）或两个亚乙烯基单元（5b）。循环伏安法揭示了两性氧化还原行为，在4和5a，5b中三甲基取代的exTTF部分具有显着强的电子给体能力。稳态和时间分辨光解技术表明，在（3a-c，4和5a，b）受到快速电子转移淬灭。通过瞬态吸收光谱法鉴定了所得的电荷分离状态，即C60 *（-）-exTTF * +。我们确定了苄腈中大约200 ns的自由基对寿命。这表明（i）exTTF * +的正电荷在整个供体上是局域化的，而不是在1