4,5-(4-pyridylethylenedithio)-1,3-dithiole-2-thione | 193015-27-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4,5-(4-pyridylethylenedithio)-1,3-dithiole-2-thione
• 英文别名: 5-(4-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione；4,5-(4-pyridylethylene)-dithio-1,3-dithiol-2-thione；5-(pyridin-4-yl)-5-hydro-6-dihydro-[1,4]dithiin-[2,3]dithio-2-thione；5-pyridin-4-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione；5-Pyridine-4-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione
• CAS: 193015-27-9
• 化学式: C₁₀H₇NS₅
• 分子量: 301.502
• InChiKey: AKAPWIUBPVTYIA-UHFFFAOYSA-N

物化性质

• 熔点：
  138 °C
• 沸点：
  476.9±55.0 °C(Predicted)
• 密度：
  1.65±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  146
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,5-(4-pyridylethylenedithio)-1,3-dithiole-2-thione 在 三异丙基亚磷酸酯 、 mercury(II) diacetate 作用下， 以 氯仿 为溶剂， 反应 3.0h， 生成 5,5',6,6'-tetrahydro-5-(4-pyridyl)-2,2'-bi([1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)
  参考文献：
  名称：

  New electron donors: BEDT-TTF derivatives bearing a pyridine group; synthesis, crystal structure, electrochemical studies and the formation of charge transfer complexes

  摘要：

  合成了含有吡啶基的双（乙烯硫醚）四硫富瓦烯（BEDT-TTF）衍生物1a、b和2a、b，并通过循环伏安法研究了它们在二氯甲烷溶液中的氧化还原电位，结果表明它们的电子给体能力弱于BEDT-TTF。化合物2b通过X射线晶体学研究，揭示了其晶体格子的柱状包装模式。探讨了这些新给体与四氰基喹啉（TCNQ）、2,3-二氯-5,6-二氰基苯-1,4-醌（DDQ）及氯化铜（CuCl₂）形成的电荷转移（CT）复合物。其中，CT复合物1b•1.1·TCNQ和1a·CuCl₂在室温下显示出半导体范围内的导电性（1b•1.1·TCNQ的σ_rt = 1.6×10⁻³ S cm⁻¹，1a·CuCl₂的σ_rt = 4.3×10⁻³ S cm⁻¹，测量是在压缩后球粒上进行的）。根据X射线光电子能谱（XPS）和导电性测量的结果，我们建议复合物1a·CuCl₂中电荷转移和配位接触共存。

  DOI：

  10.1039/a900063a
• 作为产物：
  描述：

  4-乙烯基吡啶 、 1,3-dithiol-2,4,5-trithione 以 甲苯 为溶剂， 以36%的产率得到4,5-(4-pyridylethylenedithio)-1,3-dithiole-2-thione
  参考文献：
  名称：

  一种可电聚合的吡啶功能化金双（二硫烯）配合物

  摘要：

  制备并表征了一种新的吡啶取代的二硫烯配合物 PPh4[Au(4-pdddt)2] (3)。循环伏安法显示了三个氧化还原过程，对应于双阴离子、单阴离子、中性和阳离子状态之间的相互转化，如这种类型的双（二硫烯）配合物经常呈现的那样。然而，该化合物中的最后氧化过程会产生作为电沉积膜获得的聚合物质。通过恒电位电沉积，可以获得中性金配合物 [Au(4-pdddt)2] (4) 或聚合阳离子物质的薄膜。两种薄膜在 NIR 区域都有很强的吸收，并且具有与完整金属双（二硫烯）配合物的掺入一致的特性。提出了通过形成 S-S 配位键进行聚合的机制。

  DOI：

  10.1002/ejic.201300222

文献信息

• Semiconducting Langmuir–Blodgett films of ethylenedithiotetrathiafulvalene (EDT–TTF) derivatives bearing charged and uncharged aromatic substituents
  作者：Leonid M. Goldenberg、James Y. Becker、Ofra Paz-Tal Levi、Vladimir Yu. Khodorkovsky、Lev M. Shapiro、Martin R. Bryce、John P. Cresswell、Michael C. Petty

  DOI：10.1039/a606831f

  日期：——

  Ethylenedithiotetrathiafulvalene (EDT–TTF) derivatives1–4 functionalised with a single aromatic ring have been synthesised and their Langmuir–Blodgett (LB) films have been assembled utilising only 25% molar ratio of fatty acid. For compounds 1, 3 and 4, predominantly Y-type deposition onto solid supports was observed with a transfer ratio close to unity. After doping with iodine vapour, the maximum in-plane conductivity values obtained were σ rt =10 -3 S cm -1 for 1 and 3, and 10 -5 S cm -1 for 4. LB deposition of 2 was not uniform and the conductivity value after doping was low. UV–VIS spectra of the LB films reveal the appearance of a charge-transfer (CT) band at λ max =ca. 900 nm for 1 and 4 after iodine doping. A solution of compound 3 exhibited a weak absorption band at ca. 665 nm which is assigned to an intramolecular CT band; the intensity of this band increases on exposure of the solution to light. This band is not observed in LB films of 3, neither as-deposited nor after doping. Molecular orbital calculations indicate that in the minimum energy conformation of 3, the pyridinium moiety is practically orthogonal to the TTF unit and this conformation may be obtained in solution, enabling charge-transfer to occur. A more linear conformation of 3 in the LB films may prevent intramolecular charge-transfer from occurring. Monolayers of 1, 3 and 4 were characterised by cyclic voltammetry which revealed two redox steps consistent with the formation of the EDT–TTF cation radical and dication, respectively.

  我们合成了具有单个芳香环功能的亚乙基二硫代四硫杂戊烯（EDTâTTF）衍生物1â4，并利用仅 25% 摩尔比的脂肪酸组装了它们的朗缪尔-布洛杰特（LB）薄膜。 对于化合物 1、3 和 4，在固体支撑物上观察到的主要是 Y 型沉积，转移比接近于一。在掺入碘蒸气后，1 和 3 获得的最大面内电导率值为 Ï rt =10 -3 S cm -1 ，4 为 10 -5 S cm -1 。2 的枸杞沉积不均匀，掺杂后的电导率值较低。枸杞薄膜的紫外可见光谱显示，1 和 4 在δ" max =ca.900 nm 处出现电荷转移（CT）带。化合物 3 的溶液在约 665 纳米波长处显示出一条微弱的吸收带。该吸收带的强度在溶液暴露于光线时会增加。在 3 的枸杞薄膜中，无论是沉积时还是掺杂后，都没有观察到这条带。分子轨道计算表明，在 3 的最小能量构象中，吡啶鎓分子实际上与 TTF 单元正交，这种构象可以在溶液中获得，从而实现电荷转移。通过循环伏安法对 1、3 和 4 的单层膜进行了表征，发现其中有两个氧化还原步骤分别与 EDTâTTF 阳离子自由基和二阳离子的形成相一致。
• Synthesis and Crystal Structure of the Copper(I) Chloride Complex with 4,5(4-Pyridylethylene)dithio-1,3-dithiol-2-thione and Triphenylphosphine
  作者：A. Yu. Koshevaya、V. A. Starodub

  DOI：10.1007/s11173-005-0116-0

  日期：2005.6

  The synthesis of a heteroligand complex of CuCl with triphenylphosphine and 5-pyridine-4-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (L) of composition [CuCl(PPh3)(L)](CH3 CN)}2 ( I ) is described. The crystals of complex I are triclinic: space group \(P\bar 1\), a = 8.928(2) Å, b = 13.872(3) Å, c = 14.470(3) Å, α = 72.89(3)°, β = 88.41(3)°, γ = 77.02(3)°, and Z = 2. The Cu(1) atom

  CuCl与三苯基膦和5-吡啶-4-基-5,6-二氢-[1,3]二硫代[4,5-b] [1,4]二硫代-2-硫酮的杂配体配合物的合成（L说明组成为[[CuCl（PPh 3）（L）]（CH 3 CN）} 2（ I ）的组成。配合物 I 的晶体 是三斜晶的：空间群\（P \ bar 1 \）， a = 8.928（2）Å， b = 13.872（3）Å， c = 14.470（3）Å，α= 72.89（3）° ，β= 88.41（3）°，γ= 77.02（3）°和 Z =2。Cu（1）原子具有准四面体环境，包括三苯基膦分子的磷原子，分子L的吡啶基的氮原子和两个桥联氯离子。存在非配位硫原子的事实可用于配合物 I 与软路易斯酸的进一步相互作用 。
• Pyridyl-substituted [1,3]Dithiolo-[4,5-b][1,4]dithiine-2-thiones
  作者：A. Yu. Koshevaya、V. A. Starodub、D. Fenske

  DOI：10.1007/s10593-005-0157-9

  日期：2005.3
• Cobalt(II) and nickel(II) cloride complexes with 4,5-(n-pyridylethylene)-dithio-1,3-dithiol-2-thiones (n = 2, 4)
  作者：V. A. Starodub、A. Yu. Stoesser

  DOI：10.1134/s1070328407060085

  日期：2007.6

  The NiCl2 and CoCl2 complexes with 4,5-(2-pyridylethylene)-dithio-1,3-dithiol-2-thione (L-1) and 4,5-(4-pyridylethylene)-dithio-1,3-dithiol-2-thione (L-2) were described. The L-1 ligand shows bidentate coordination through the pyridyl N atoms and the thiol S atoms in a tetrahedral [CoCl2(L-1)] complex (I) and in an octahedral [NiCl2(L-1)2](MeCN)(2) complex (II). The L-2 ligand exhibits monodentate coordination through the pyridyl N atom in tetrahedral complexes [CoCl2(L-2)(2) (III) and [NiCl2(L-2)(2)] (IV). Complexes I, III, IV in crystal state are octahedral due to extra coordination of the thione S atoms or the chloride bridges responsible for the polymeric structure. The structure of the complex II center dot CH2Cl2 was determined by X-ray diffraction analysis. The crystals are monoclinic, space group P2(1)/c, a = 11.895(2) angstrom, b = 13.374(3) angstrom, c = 21.873(4) angstrom, beta = 95.30(3)degrees, Z = 2. The Ni atom has quasi-tetrahedral surrounding due to two chloride ions and two L-1 ligands coordinated through the pyridyl N atoms and the thiol S atoms.