3-[2-(4,5-ethylenedisulfanyl-1,3-dithiol-2-ylidene)-5-methylsulfanyl-1,3-dithiol-4-ylsulfanyl]propanenitrile | 177160-54-2

• 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: 3-[2-(4,5-ethylenedisulfanyl-1,3-dithiol-2-ylidene)-5-methylsulfanyl-1,3-dithiol-4-ylsulfanyl]propanenitrile
• 英文别名: 2-(2-cyanoethylthio)-6,7-(ethylenethio)-3-methylthiotetrathiafulvalene；3-[[2-(5,6-Dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 177160-54-2
• 化学式: C₁₂H₁₁NS₈
• 分子量: 425.754
• InChiKey: QJOGQVDCSCSVHZ-UHFFFAOYSA-N

物化性质

• 熔点：
  97-98 °C(Solv: methanol (67-56-1))
• 沸点：
  524.4±50.0 °C(Predicted)
• 密度：
  1.66±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  226
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3-[2-(4,5-ethylenedisulfanyl-1,3-dithiol-2-ylidene)-5-methylsulfanyl-1,3-dithiol-4-ylsulfanyl]propanenitrile 在 氢氧化钾 、 Bu₃P(C₁₁₆H₃₃)Br 、 sodium ethanolate 、 一水合肼 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 52.0h， 生成 2-[2-(5,6-Dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-5-methylsulfanyl-[1,3]dithiol-4-ylsulfanyl]-ethylamine
  参考文献：
  名称：

  Synthesis of New Functionalized π-Electron Donors: Primary Hydroxy and Primary Amino Multisulfur Tetrathiafulvalenes

  摘要：

  本文描述了新的主羟基和氨基四硫富瓦烯的合成。羟基衍生物3a和3b由受保护的TTF硫醇合成，而氨基衍生物14a、14b和17则由相应的羟基TTF通过加布里埃尔合成或叠氮化物还原制备。本文还报道了新的双亲性双（羟基）和双（氨基）TTF的合成。

  DOI：

  10.1055/s-1997-1321
• 作为产物：
  描述：

  4,5-双(2-氰乙基硫代)-1,2-二硫醇-2-酮 在 cesium hydroxide 、 亚磷酸三乙酯 作用下， 反应 2.0h， 生成 3-[2-(4,5-ethylenedisulfanyl-1,3-dithiol-2-ylidene)-5-methylsulfanyl-1,3-dithiol-4-ylsulfanyl]propanenitrile
  参考文献：
  名称：

  Sequential Functionalisation of Bis-Protected Tetrathiafulvalene-dithiolates

  摘要：

  据报道，2-氰乙基是 2-硫酮-1,3-二硫环戊-4,5-二硫酸盐和四硫富戊烯-硫酸盐的多功能保护基团。通过 4,5-双（2-氰乙基硫代）-1,3-二硫代-2-酮 5 与 1,3-二硫代-2-硫酮 2b-h 和 2j 在亚磷酸三乙酯中的交叉偶联，实现了双保护的 2-硫酮-1,3-二硫代-4,5-二硫酸盐和双保护的四噻吩富戊烯-2,3-二硫酸盐的单脱保护，产率非常高。在二甲基甲酰胺溶液中，使用一水合氢氧化铯在甲醇中进行选择性单脱保护，从双保护起始材料中生成单硫醇酯。随后用碘甲烷淬火，得到甲硫基取代的 1,3-二硫杂-2-硫酮 2i 和四硫杂戊烯 8，产量接近定量。报告了空气稳定的四硫富戊烯硫代铯 10 的 X 射线晶体结构。这是首次测定四硫富戊烯硫酸盐的单晶 X 射线晶体结构。

  DOI：

  10.1055/s-1996-4216

文献信息

• Fabrication and Operation of Monolayer Mott FET at Room Temperature
  作者：Fan Yang、Masayuki Suda、Hiroshi M. Yamamoto

  DOI：10.1246/bcsj.20170233

  日期：2017.11.15

  Self-assembled monolayer FET based on a TTF derivative is described (FET = field-effect-transistor, TTF = tetrathiafulvalene). The molecule is anchored on an alumina dielectric layer through covalent bonding of a phosphonic acid linker. A p-type monolayer FET device is achieved and subsequent chemical doping of this monolayer with F4TCNQ dopants results in an ambipolar device. (F4TCNQ = 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane) Several strange behaviors including a gate voltage shift upon doping seem to be consistent with organic monolayer Mott FET. Finally, temperature dependence of the FET performance, which also fit the anticipated Mott FET behavior, is discussed.

  本文描述了一种基于TTF衍生物的自组装单分子层场效应晶体管（FET = 场效应晶体管，TTF = 四硫富瓦烯）。该分子通过磷酸酯连接子通过共价键固定在铝氧化物绝缘层上。实现了p型单分子层FET器件，随后对该单分子层进行F4TCNQ掺杂，结果形成了双极器件。（F4TCNQ = 2,3,5,6-四氟-7,7,8,8-四氰基喹啉二甲烷）包括掺杂后栅电压偏移在内的几种奇特行为似乎与有机单层MoTT FET一致。最后，讨论了FET性能的温度依赖性，这也符合预期的MoTT FET行为。
• Luminescence Switching of a Cyclometalated Iridium(III) Complex through a Redox-active Tetrathiafulvalene-based Ligand
  作者：Chun-Hu Xu、Wei Sun、Chao Zhang、Can Zhou、Chen-Jie Fang、Chun-Hua Yan

  DOI：10.1002/chem.200901483

  日期：2009.9.7

  OFF‐ON‐OFF: By reversible modulation of the oxidation states of the synthesised IrIII complex seen here, distinct electron‐transfer efficiencies are exhibited and, remarkably, affect the properties of the IrIII core in the excited state. Thereby, a redox‐controlled “OFF‐ON‐OFF” molecular phosphorescence switch is realized.

  OFF-ON-OFF：通过对合成的Ir III络合物的氧化态进行可逆调节，可以显示出不同的电子转移效率，并且显着影响激发态的Ir III核的性能。由此，实现了氧化还原控制的“ OFF-ON-OFF”分子磷光开关。
• Synthesis and electrochemical properties of tetrathiafulvalene derived amino acids and peptides
  作者：Susan Booth、Emma N. K. Wallace、Kavita Singhal、Philip N. Bartlett、Jeremy D. Kilburn

  DOI：10.1039/a800759d

  日期：——

  A synthetic route to a tetrathiafulvalene (TTF) derived aspartic acid derivative 18, with suitable orthogonal protecting groups has been developed. The aspartic acid derivative 18 can be used in the synthesis of peptides, as exemplified by the synthesis of di-, tri- and tetra-peptides 21–23. Preliminary electrochemical studies of these novel peptides indicate that they may well undergo conformational reorganisation upon oxidation of the TTF moieties.

  我们开发出了一条合成四噻吩（TTF）衍生天冬氨酸衍生物 18 的路线，并带有合适的正交保护基团。天冬氨酸衍生物 18 可用于合成肽，例如合成二肽、三肽和四肽 21-23。对这些新型肽进行的初步电化学研究表明，在 TTF 分子被氧化后，它们很可能会发生构象重组。
• Tetrathiafulvalene Thiolates: Important Synthetic Building Blocks for Macrocyclic and Supramolecular Chemistry
  作者：Klaus Simonsen、Jan Becher

  DOI：10.1055/s-1997-1001

  日期：1997.11

  The Preparation of rather complex molecular assemblies can now be accomplished by using a complete set of tetrathiafulvalene (TTF) based building blocks. The facile deprotection of the 2-cyanoethyl group, a versatile protecting group for 1,3-dithiolium-2-thione-4,5-dithiolaes and TTF-thiolates have proven to be a viable method for the incorporation of TTF units into macrocyclic and supramolecular compounds. Especially the stepwise protection-deprotection methodology have been used extensively by our group for the preparation of two and three dimensional macrocyclic (mono-, bis- and tricyclic) as well as TTF-based supramolecular systems. The generation, utilization and scope of the generated thiolates are illustrated by several examples: Dendrimeric and oligo-TTF's, three dimensional tetrathafulvalenophanes, TTF-containing catenanes and rotaxanes and donor acceptor systems based on TTF as the donating portion.

  现在，通过使用一整套基于四噻吩（TTF）的构建模块，可以制备相当复杂的分子组装体。2-Cyanoethyl 基团是 1,3-二硫代-2-硫酮-4,5-二硫环戊烯和 TTF-硫代酸酯的通用保护基团，对该基团进行简易脱保护已被证明是将 TTF 单元加入大环和超分子化合物的可行方法。特别是分步保护-保护方法已被我们小组广泛用于制备二维和三维大环（单环、双环和三环）以及基于 TTF 的超分子体系。我们通过几个实例来说明所生成的硫代化合物的生成、利用和应用范围：树枝状和低聚 TTF、三维四富戊烯烷、含 TTF 的卡替烷和轮烷以及以 TTF 为捐献部分的捐献受体系统。
• Synthesis and study of radical cation salts and TCNQ charge transfer complexes of a series of tetrathiafulvalenes (TTF) substituted by one or two hydroxylated side chain(s): –SCH2CH2OH
  作者：Jean-Pierre Legros、Françoise Dahan、Laurent Binet、Carole Carcel、Jean-Marc Fabre

  DOI：10.1039/b003009k

  日期：——

  Unsymmetrically substituted tetrathiafulvalene derivatives containing hydroxy group(s) on side-chain(s) have been synthesized from cyano precursors via either a cross-coupling reaction or a Wittig-type condensation. As deduced from cyclic voltammetry data, the electron donor properties of the obtained compounds have been found to be similar to those of BEDTTTF. A series of radical cation salts derived from these donors has been obtained by electrocrystallization and charge transfer complexes have been prepared chemically by using TCNQ as an electron acceptor. The electrical conductivity of these phases ranges from 3 × 10−2 to 7 × 10−7 S cm−1 which is consistent with their structural features. X-Ray structural analysis of three of the radical cation salts with monovalent closed-shell anions (Br−, ClO4−) indicates a 1 ∶ 1 stoichiometry which implies that, in each case, the donor has been oxidized to the D+ state. In the same way, a crystal structure made of stacks where the donor and the acceptor molecules alternate has been found for a charge transfer complex between TCNQ and a donor derived from EDTTTF. The crystal structure of one of the donors indicates that the flexibility of the hydroxylated side chains appears as a favourable feature for the formation of hydrogen bonds.

  侧链上含有羟基的不对称取代的四硫富瓦烯衍生物已由氰基前体通过交叉偶联反应或维蒂希型缩合合成。根据循环伏安法数据推断，所得化合物的电子供体性质与 BEDTTTF 相似。通过电结晶获得了一系列由这些供体衍生的自由基阳离子盐，并使用 TCNQ 作为电子受体化学制备了电荷转移络合物。这些相的电导率范围为3×10×2至7×10×7S cm×1，这与其结构特征一致。三种自由基阳离子盐与一价闭壳阴离子（Br-、ClO4-）的 X 射线结构分析表明，化学计量为 1 - 1，这意味着在每种情况下，供体已被氧化为D+状态。以同样的方式，对于 TCNQ 和源自 EDTTTF 的供体之间的电荷转移络合物，发现了由供体和受体分子交替的堆叠组成的晶体结构。其中一个供体的晶体结构表明，羟基化侧链的柔性似乎是形成氢键的有利特征。