2,3-bis(2-cyanoethylthio)-6,7-bis(hexylthio)tetrathiafulvalene | 562809-83-0

• 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: 2,3-bis(2-cyanoethylthio)-6,7-bis(hexylthio)tetrathiafulvalene
• 英文别名: 3-[[2-[4,5-Bis(hexylsulfanyl)-1,3-dithiol-2-ylidene]-5-(2-cyanoethylsulfanyl)-1,3-dithiol-4-yl]sulfanyl]propanenitrile；3-[[2-[4,5-bis(hexylsulfanyl)-1,3-dithiol-2-ylidene]-5-(2-cyanoethylsulfanyl)-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 562809-83-0
• 化学式: C₂₄H₃₄N₂S₈
• 分子量: 607.075
• InChiKey: IVGQAYSSNYHALW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  34
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  250
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3-bis(2-cyanoethylthio)-6,7-bis(hexylthio)tetrathiafulvalene 在 cesiumhydroxide monohydrate 、 2-溴乙醇 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.42h， 以59%的产率得到2,3-bis(2-hydroxyethylthio)-6,7-bis(hexylthio)tetrathiafulvalene
  参考文献：
  名称：

  Synthesis and electron-donating properties of novel norphthalocyanines containing thiacrown ether-linked tetrathiafulvalene moieties

  摘要：

  A novel magnesium-base and metal-free norphthalocyanine (6 and 7) containing peripheral thiacrown ether-linked tetrathiafulvalene moieties have been synthesized and fully characterized. Electrochemical investigations showed two quasi-reversible one-electron oxidation waves, one irreversible one-electron oxidation wave and two irreversible one-electron reduction waves, indicating that these triads are good pi-electron donors. Triad 6 reacted with 2,3,5,6-tetrafluoro-7,7,8,8-tetra-cyanoquinodimethane (F(4)TCNQ) to form a charge transfer complex that exhibited absorption bands in the vicinity of 750 and 960 nm. Compound 6 showed evident intramolecular charge transfer interactions in ground states and these may be explained on the basis of the density functional theory. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2015.12.089
• 作为产物：
  描述：

  溴己烷 在 亚磷酸三乙酯 作用下， 以 乙腈 为溶剂， 反应 8.0h， 生成 2,3-bis(2-cyanoethylthio)-6,7-bis(hexylthio)tetrathiafulvalene
  参考文献：
  名称：

  具有戊硫基和己硫基的不对称有机金属金 (III)-二噻吩配合物表现出独特的热结构相变

  摘要：

  合成了两种含有戊硫基和己硫基的金 (III)-二硫烯络合物，以开发具有热结构相变的分子材料。戊硫基络合物的熔点仅为 198 °C。己硫基络合物在两个结晶相和各向同性液体之间表现出多重相变。高温区的晶体以缓慢的结晶速率生长。

  DOI：

  10.1002/ejic.202300017

文献信息

• Calix[4]arenes with 1,2- and 1,3-upper rim tetrathiafulvalene bridges
  作者：Matthias H. Düker、Felix Kutter、Thomas Dülcks、Vladimir A. Azov

  DOI：10.1080/10610278.2013.872245

  日期：2014.8.3

  Herein we report the synthesis of several calix[4]arene derivatives with tetrathiafulvalene bridges at the upper rim. Calix[4]arene-tetrathiafulvalene (TTF) conjugates 4a–d, fixed in cone conformation and comprising two smaller 1,2-bridges, were prepared by cyclisation of tetrakis-chloromethylated calix[4]arene 1 with 2,3-dithiolates of TTFs. Larger calix[4]arene-TTF macrocycles 14 and 15, also in

  在这里，我们报告了几种杯[4]芳烃衍生物的合成，在上缘具有四硫富瓦烯桥。杯[4] 芳烃-四硫富瓦烯 (TTF) 共轭物 4a-d，固定为锥形构象并包含两个较小的 1,2-桥，通过四氯甲基化杯 [4] 芳烃 1 与 2,3-二硫醇盐的环化制备TTF。较大的杯 [4] 芳烃-TTF 大环 14 和 15，同样为锥形构象，包含 1,3-桥，通过用双溴甲基化杯 [4] 环化 TTF 的 2,6- 和 2,7-二硫醇盐合成芳烃 7. 使用循环伏安法表征新杯[4]芳烃-TTF缀合物的氧化还原特性。
• Synthesis, spectroscopic, and electrochemical properties of three tetrathiafulvalenes attached to perylene
  作者：Haixiao Qiu、Chengyun Wang、Jinfeng Xu、Guoqiao Lai、Yongjia Shen

  DOI：10.1007/s00706-008-0863-y

  日期：2008.11

  donor–acceptor dyads 1 – 3 comprising of a tetrathiafulvalene ( TTF ) unit linked with perylene by a simple σ-bond were synthesized and characterized. Spectroscopy and cyclic voltammetry provided an indication that intramolecular charge-transfer interactions in their ground states between TTF and perylene for dyads 1 – 3 are negligible. Compared with the compound perylene, dyads 1 – 3 exhibited large fluorescence

  三个供体-受体成对层 1 - 3 ，其包括硫富瓦烯（的 TTF 通过简单的σ键与苝连接）单元被合成和表征。光谱和循环伏安法提供的指示在它们之间的基态的分子内电荷转移相互作用 TTF 和苝为成对层 1 - 3 是可忽略的。与化合物苝相比，成对层 1 - 3 表现出大的荧光淬灭，这可能归因于间光诱导电子转移相互作用 TTF 处于兴奋状态和苝单元。
• Synthesis and properties of a tetrathiafulvalene–perylene tetracarboxylic diimide–tetrathiafulvalene dyad
  作者：Yu Zhang、Liang-Zhen Cai、Cheng-Yun Wang、Guo-Qiao Lai、Yong-Jia Shen

  DOI：10.1039/b719844b

  日期：——

  A donor–acceptor–donor dyad 4 involving 2-sulfur-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene (TTF) as a donor attached directly to N,N′-dibutylperylene-3,4,9,10-tetracarboxylic diimide (PDI) as an acceptor was synthesized by condensation of N,N′-dibutyl-1,6-dibromo-3,4,9,10-perylenetetracarboxylic diimide and 2-(2-cyanoethylthio-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene. The cyclic voltammetric (CV) data implied significant intramolecular interaction and the absorption spectrum indicated that there was an intramolecular charge transfer (ICT) interaction between TTF and PDI moieties in dyad 4. Comparing with PDI 13, the fluorescence emission intensity of dyad 4 was quenched almost quantitatively, which might result from the photo-induced electron transfer (PET) interaction between the PDI and TTF moieties in dyad 4. The fluorescence intensity of dyad 4 could be reversibly modulated by sequential oxidation and reduction of the TTF unit using chemical methods. Thus dyad 4 can be regarded as a new reversible fluorescence-redox dependent molecular switch.

  通过缩合 N,N²-二丁基-1,6-二溴-3,4,9,10-四羧酸二亚胺（PDI）作为受体，合成了供体-受体-受体四元化合物、通过缩合 N,N²-二丁基-1,6-二溴-3,4,9,10-过烯四羧酸二亚胺和 2-(2-氰基乙硫基-3-甲硫基-6,7-双(己硫基)四硫代富勒烯，合成了作为受体的 10-四羧酸二亚胺（PDI）。循环伏安（CV）数据表明存在显著的分子内相互作用，而吸收光谱则表明在对偶 4 中，TTF 和 PDI 分子之间存在分子内电荷转移（ICT）相互作用。与 PDI 13 相比，染料 4 的荧光发射强度几乎被定量淬灭，这可能是染料 4 中 PDI 和 TTF 分子之间的光诱导电子转移（PET）作用所致。使用化学方法依次氧化和还原 TTF 单元，可以可逆地调节染料 4 的荧光强度。因此，共轭物 4 可被视为一种新的可逆荧光-氧化还原依赖性分子开关。
• New tetrathiafulvalene fused-naphthalene diimides for solution-processible and air-stable p-type and ambipolar organic semiconductors
  作者：Luxi Tan、Yunlong Guo、Yang Yang、Guanxin Zhang、Deqing Zhang、Gui Yu、Wei Xu、Yunqi Liu

  DOI：10.1039/c2sc20303k

  日期：——

  New conjugated electron donor–acceptor molecules with tetrathiafulvalene (TTF) fused-naphthalene diimide frameworks (1–6) are synthesized and investigated. The NDI cores are flanked by TTF and 2-(1,3-dithiol-2-ylidene)malonitrile moieties within 1–3, whereas compounds 4–6 contain two TTF moieties. Based on cyclic voltammetric and absorption spectral studies, the LUMO and HOMO energies of 1–3 are estimated to be ca. −4.3 eV and ca. −5.1 eV, and those of 4–6 are ca. −4.1 eV and ca. −5.0 eV, respectively. These values are consistent with theoretical calculations. Thin films of 1–6 are easily prepared with the spin-coating technique and the resulting OFETs are successfully fabricated with conventional procedures. The OFETs results reveal that compounds 1–3 behave as ambipolar semiconductors and 4–6 as p-type semiconductors. Among 1–3, compound 3 exhibits relatively high hole and electron mobilities in air, reaching 0.03 and 0.003 cm2 V−1 s−1, respectively, after annealing at 160 °C. The OFET based on a thin film of 5 shows the best performance with μh = 0.31 cm2 V−1 s−1, Ion/off = 104 among compounds 4–6 after annealing at 160 °C. The thin films of 1–6 are investigated with XRD and AFM, and the data can well interpret the variation of carrier mobilities of 1–6 after annealing. Moreover, the influences of alkyl chains in 1–6 on the intermolecular arrangements and carrier mobilities are also discussed.

  合成并研究了具有四噻富戊二烯（TTF）融合萘二亚胺框架（1-6）的新型共轭电子供体-受体分子。在 1-3 号化合物中，NDI 核心的两侧分别是 TTF 和 2-(1,3- 二硫醇-2-亚基)丙二腈分子，而 4-6 号化合物则含有两个 TTF 分子。根据循环伏安法和吸收光谱研究，估计 1-3 的 LUMO 和 HOMO 能量分别约为 -4.3 eV 和 -4.3 eV。4.3 eV 和 -5.1 eV。5.1 eV，4-6 的能量分别约为 -4.1 eV 和 -5.1 eV。-4.1eV和-5.0 eV。这些数值与理论计算结果一致。利用旋涂技术可以轻松制备 1-6 薄膜，并通过传统方法成功制造出 OFET。OFET 的结果表明，化合物 1-3 表现为双极性半导体，化合物 4-6 表现为 p 型半导体。在 1-3 种化合物中，化合物 3 在空气中表现出相对较高的空穴和电子迁移率，在 160 °C 退火后分别达到 0.03 和 0.003 cm2 V-1 s-1。基于 5 薄膜的 OFET 在 160 °C 退火后，在 4-6 化合物中显示出最佳性能，μh = 0.31 cm2 V-1 s-1，离子/关 = 104。利用 XRD 和原子力显微镜对 1-6 薄膜进行了研究，这些数据可以很好地解释 1-6 在退火后载流子迁移率的变化。此外，还讨论了 1-6 中烷基链对分子间排列和载流子迁移率的影响。
• Synthesis of electrochemically responsive TTF-based molecular tweezers: evidence of tight intramolecular TTF pairing in solution
  作者：Vladimir A. Azov、Rafael Gómez、Johannes Stelten

  DOI：10.1016/j.tet.2007.11.110

  日期：2008.2

  We report the synthesis and conformational studies of TTF-containing molecular tweezers based on a 1,2,4,5-tetramethylbenzene scaffold. In the neutral form the tweezers are expected to adopt the closed conformation, while, upon oxidation, the open conformation should be preferred due to electrostatic repulsion between the oxidized TTF moieties. Cyclic voltammetry studies demonstrate electronic pairing with formation of mixed-valence [TTF](2)(+center dot) species and opening of the tweezers upon the full oxidation of the TTF groups. Variable-temperature (VT) NMR studies evidence tight intramolecular TTF pairing at low temperature. Molecular modeling studies showed clear preference for an open conformation of tweezers in a fully oxidized state. (C) 2007 Elsevier Ltd. All rights reserved.