4,4',5,5'-tetrakis(hexylsulfanyl)-2,2'-bi-1,3-dithiol | 106920-30-3

• 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: 4,4',5,5'-tetrakis(hexylsulfanyl)-2,2'-bi-1,3-dithiol
• 英文别名: tetrakis(hexylthio)tetrathiafulvalene；2,3,6,7-tetrakis(hexylthio)tetrathiafulvalene；2-[4,5-Bis(hexylsulfanyl)-1,3-dithiol-2-ylidene]-4,5-bis(hexylsulfanyl)-1,3-dithiole
• CAS: 106920-30-3
• 化学式: C₃₀H₅₂S₈
• 分子量: 669.271
• InChiKey: ZKAHMOOIUNETAG-UHFFFAOYSA-N

物化性质

• 熔点：
  26-28 °C
• 沸点：
  637.1±55.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  14.7
• 重原子数：
  38
• 可旋转键数：
  24
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  202
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4,4',5,5'-tetrakis(hexylsulfanyl)-2,2'-bi-1,3-dithiol 在 六氟锑酸亚硝 作用下， 以 二氯甲烷-D2 为溶剂， 生成 2,3,6,7-tetrakis(hexylthio)tetrathiafulvalene bis(hexafluoroantimonate)
  参考文献：
  名称：

  Synthesis of electrochemically responsive TTF-based molecular tweezers: evidence of tight intramolecular TTF pairing in solution

  摘要：

  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.

  DOI：

  10.1016/j.tet.2007.11.110
• 作为产物：
  描述：

  双(羰基二硫代)四硫富瓦烯 以70%的产率得到
  参考文献：
  名称：

  WU, PEIJI;SAITO, GUNZI;IMAEDA, KENICHI;SHI, ZURONG;MORI, TAKEHIKO;ENOKI, +, CHEM. LETT., 1986, N 4, 441-444

  摘要：

  DOI：

文献信息

• Tetrathiafulvalene (TTF)-Bridged Resorcin[4]arene Cavitands: Towards New Electrochemical Molecular Switches
  作者：Markus Frei、François Diederich、Rolando Tremont、Tanya Rodriguez、Luis Echegoyen

  DOI：10.1002/hlca.200690194

  日期：2006.9

  We report the synthesis of novel resorcin[4]arene-based cavitands featuring two extended bridges consisting of quinoxaline-fused TTF (tetrathiafulvalene) moieties. In the neutral form, these cavitands were expected to adopt the vase form, whereas, upon oxidation, the open kite geometry should be preferred due to Coulombic repulsion between the two TTF radical cations (Scheme 2). The key step in the

  我们报告了新颖的基于间苯二酚[4]芳烃的cavitands的合成，具有两个由喹喔啉融合的TTF（四硫富瓦烯）部分组成的延伸桥。在中性形式下，预计这些空洞将采用花瓶形式，而在氧化时，由于两个TTF自由基阳离子之间的库仑排斥性，开放风筝的几何形状应是优选的（方案2）。制备这些新型分子开关的关键步骤是大环双（1,3-二硫醇-2-硫酮）与2当量之间的P（OEt）3介导的偶联。合适的1，3-二硫醇-2-酮的混合物。在将这一策略成功应用于制备单TTF-cavitand 3（方案3），进行双-TTF衍生物2（方案4）和19-（方案5）的合成。但是，目标化合物由于其不溶性而无法分离。在用长的烷基链装饰辛醇碗和TTF空腔边缘时，除了少量的具有高度扭曲的TTF桥的新型笼型化合物25a外，最终获得了可溶的bis-TTF cavitand 23（方案6）。相反25a中，深穴状23所经历可逆花瓶风筝在从293将温度
• UNCAPPED ALKYLTHIO SUBSTITUTED TETRATHIAFULVALENES (TTC_n-TTF) AND THEIR CHARGE TRANSFER COMPLEXES
  作者：Peiji Wu、Gunzi Saito、Kenichi Imaeda、Zurong Shi、Takehiko Mori、Toshiaki Enoki、Hiroo Inokuchi

  DOI：10.1246/cl.1986.441

  日期：1986.4.5

  A series of tetraalkylthio substituted tetrathiafulvalenes (TTCn-TTF) was prepared. The syntheses, molecular and crystal structures, and physical properties of TTCn-TTF reveal marked differences from those of BEDT-TTF. The conformational change of TTC1-TTF molecule on the formation of charge transfer complexes and the mode of the S…S contacts are described in connection with those of BEDT-TTF compounds

  制备了一系列四烷硫基取代的四硫富瓦烯 (TTCn-TTF)。TTCn-TTF 的合成、分子和晶体结构以及物理性质显示出与 BEDT-TTF 的显着差异。TTC1-TTF 分子在形成电荷转移复合物时的构象变化和 S…S 接触的模式与 BEDT-TTF 化合物的结构变化有关。
• Synthesis and electrochemistry of soluble double-bridged tetrathiafulvalene (TTF)-p-benzoquinone dyads
  作者：Mar González、Beatriz Illescas、Nazario Martín、JoséL. Segura、Carlos Seoane、Michael Hanack

  DOI：10.1016/s0040-4020(98)83022-6

  日期：1998.3

  unsymmetrically substituted TTF derivatives as precursor for the preparation of novel TTF-based donor-bridge-acceptor dyads is reported. Substitution on the acceptor p-benzoquinone moiety has a strong influence on the reduction potentials in compounds 18 which, however, do not show the presence of a charge transfer band in the electronic spectra. The cyclic voltammetry measurements reveal two oxidation waves

  据报道，新型可溶性不对称取代的TTF衍生物作为前体，用于制备新型的基于TTF的供体-桥-受体二元体。受体对-苯醌部分上的取代对化合物18中的还原电位有很大的影响，然而，在电子光谱中没有显示出电荷转移带的存在。循环伏安法测量揭示了16和17中TTF部分的两个氧化波和分配给氢醌部分的第三个氧化波。化合物18除了TTF氧化波，还显示存在与醌部分相对应的还原波。光谱电化学研究表明阳离子自由基的逐步形成和TTF片段的阳离子化。
• Synthesis and electrochemistry of a soluble double-bridged tetrathiafulvalene (TTF)-p-benzoquinone from novel unsymmetrical TTFs
  作者：JoséL. Segura、Nazario Martín、Carlos Seoane、Michael Hanack

  DOI：10.1016/0040-4039(96)00304-8

  日期：1996.4

  The synthesis of novel unsymmetrically substituted TTFs and the subsequent transformation into a donor-σ-acceptor system is reported; The CV and the spectroelectrochemical studies reveal the presence of both electroactive moieties.

  报道了新颖的不对称取代的TTF的合成以及随后转化为供体-σ-受体系统；CV和光谱电化学研究揭示了两个电活性部分的存在。
• Synthesis of Pyrazinoporphyrazine Derivatives Functionalised with Tetrathiafulvalene (TTF) Units: X-Ray Crystal Structures of Two Related ttf Cyclophanes and Two Bis(1,3-Dithiole-2-Thione) Intermediates
  作者：C. S. Wang、M. R. Bryce、A. S. Batsanov、J. A. K. Howard

  DOI：10.1002/chem.19970031018

  日期：1997.10

  AbstractThe pyrazinoporphyrazine system 13 (metal‐free, zinc and copper derivatives) has been synthesised by tetramerisation of 2,3‐dicyanopyrazine monomer unit 10. The structure of 13a‐c has been established by 1H NMR spectroscopy, UV/Vis spectrophotometry, MALDI‐TOF mass spectrometry, cyclic voltammetry and differential pulse voltammetry. The electrochemical redox behaviour of 13a‐c is strongly solvent dependent. The expected two‐stage oxidation of the tetrathiafulvalene (TTF) units of 13a‐c was observed in a range of solvents; in addition, oxidation and reduction of the pyrazinoporphyrazine core of the metal‐free derivative 13a was detected in benzonitrile. On excitation of 13 in the Q‐band region no fluorescence was observed, which is presumably the consequence of intramolecular charge transfer between the TTF moieties and the excited state of the central porphyrazine. Molecular modelling studies on 13a and 13c are reported. During the course of this work, the novel TTF macrocycles 11 and 20 were synthesised; their X‐ray crystal structures reveal severely bent TTF units, the conformations of which are discussed in detail. The X‐ray crystal structures of the bis(1,3‐dithiole) systems 15 and 18 have also been determined.