4,5-diiodo-4',5'-(ethylenedithio)tetrathiafulvalene | 163774-27-4

• 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: 4,5-diiodo-4',5'-(ethylenedithio)tetrathiafulvalene
• 英文别名: 2-(4,5-Diiodo-1,3-dithiol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine
• CAS: 163774-27-4
• 化学式: C₈H₄I₂S₆
• 分子量: 546.325
• InChiKey: NWQMZDWLHIYSKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  152
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  7,7,8,8-四氰基对苯二醌二甲烷 、 4,5-diiodo-4',5'-(ethylenedithio)tetrathiafulvalene 以 二氯甲烷 、 乙腈 为溶剂， 反应 336.0h， 生成
  参考文献：
  名称：

  电荷辅助的卤素键合：具有可变离子性的供体-受体复合物

  摘要：

  一系列碘衍生的四硫富瓦烯和四氰基喹二甲烷衍生物（EDT-TTFI 2）2（TCNQF n），n = 0–2衍生的一系列同构电荷转移络合物的结构和电子研究清楚地揭示了电荷辅助的卤素键。可变的离子度。碘化硫富瓦烯衍生物，EDT-TTFI 2，用甲烷（TCNQ）和它的增加的还原电位（TCNQF，TCNQF的衍生物联营2通过高度定向C）I⋅⋅⋅N≡C卤素键相互作用。使用较少氧化的TCNQ受体，可以分离出中性和绝缘性的电荷转移络合物，而使用较高氧化性的TCNQF 2受体，可以发现离子的，高传导性的电荷转移盐，其化学计量比为2：1，中间结构为TCNQF复杂，其中冷却时发生中性离子转变。的电荷转移的程度以及C之间的相关性 I⋅⋅⋅N≡C卤素粘结强度是从三个同构复合物的结构在温度比较建立从300到20 K，因此证明静电的重要性在卤素键相互作用中。（EDT-TTFI 2）2中的中性离子转化（TCNQF）

  DOI：

  10.1002/chem.201302507
• 作为产物：
  描述：

  ethylenedithiotetrathiafulvalene 以80%的产率得到
  参考文献：
  名称：

  Kux Ulrich, Suzuki Hironori, Sasaki Shigeru, Iyoda Masahiko, Chem. Lett, (1995) N 3, S 183-184

  摘要：

  DOI：

文献信息

• Hal⋯Hal interactions in a series of three isostructural salts of halogenated tetrathiafulvalenes. Contribution of the halogen atoms to the HOMO–HOMO overlap interactions
  作者：Benoît Domercq、Thomas Devic、Marc Fourmigué、Pascale Auban­Senzier、Enric Canadell

  DOI：10.1039/b100103p

  日期：——

  The halogenated tetrathiafulvalenes, Br2-EDT-TTF and I2-EDT-TTF were prepared by the coupling route from the corresponding 4,5-dibromo- or 4,5-diiodo-1,3-dithiole-2-thione. In the isostructural series, (Br2-EDT-TTF)2IBr2, (Br2-EDT-TTF)2I3 and (I2-EDT-TTF)2I3, noted Br2/IBr2, Br2/I3 and I2/I3 respectively, short (3.42–3.60 Å) and directional Hal⋯Hal interactions are identified between donor molecules and with the anions, stabilising rare β′ phases. These interactions play not only a structural role but also contribute to the electronic dispersion thanks to sizeable coefficients on the halogen atoms in the HOMOs of Br2-EDT-TTF and I2-EDT-TTF. The three salts behave as Mott insulators as reflected by a high room temperature conductivity (0.5 S cm−1) with an activation energy which increases in the order Br2/IBr2 (730 K), Br2/I3 (1260 K), I2/I3 (1330 K) and a weak magnetic susceptibility, which decreases abruptly below 150 K with no sign of an antiferromagnetic ground state.

  卤化的四硫富瓦烯 Br2-EDT-TTF 和 I2-EDT-TTF 通过相应的 4,5-二溴或 4,5-二碘-1,3-二硫醇-2-酮的偶联途径制备。在同构系列中，(Br2-EDT-TTF)2IBr2、(Br2-EDT-TTF)2I3 和 (I2-EDT-TTF)2I3，分别记为 Br2/IBr2、Br2/I3 和 I2/I3，鉴定出短程（3.42–3.60 Å）且定向的卤-卤相互作用存在于供体分子与阴离子之间，从而稳定了稀有的 β′ 相。这些相互作用不仅发挥结构作用，还通过 Br2-EDT-TTF 和 I2-EDT-TTF 中 HOMOs 上卤素原子的显著系数对电子分散产生贡献。这三种盐表现出莫特绝缘体特性，其高室温电导率（0.5 S cm⁻¹）反映出其活化能按 Br2/IBr2 (730 K)、Br2/I3 (1260 K) 和 I2/I3 (1330 K) 的顺序增加，且具有较弱的磁化率，在 150 K 以下急剧下降，未出现反铁磁基态的迹象。
• Anionic Layered Networks Reconstructed from [Cd(SCN)₃]_∞⁻ Chains in Pseudo One-Dimensional Conducting Salts of Halogenated Tetrathiafulvalenes
  作者：Marc Fourmigué、Pascale Auban-Senzier

  DOI：10.1021/ic801207v

  日期：2008.11.3

  an unconventional rho = 0.4 in 2. They behave as semiconductors with sigma RT = 0.67 and 33 S cm(-1) and activation energies of 330 and 370 K for 1 and 2, respectively. Compared with a 1:3 Cd/SCN ratio of the starting electrolyte, the reconstructed, thiocyanate (SCN)-deficient motifs [Cd3(NCS)8](2-) and [Cd5(SCN)14](4-) organize into layered hollow structures with cavities filled by solvent molecules

  在聚合物1D [Et4N] [Cd（SCN）3]存在下，二碘-和二溴-乙烯-二硫代四硫代富瓦烯（EDT-TTFI2和EDT-TTFBr2）的电结晶提供了两种不同的盐，配制成[EDT-TTF- I2] 4 [Cd3（NCS）8] x CH3CN x H2O（1）和[EDT-TTF-Br2] 10 [Cd5（SCN）14] x 2 TCE（2），其特征在于部分分离二维氧化的供体分子和结合了嵌入式溶剂分子的聚合阴离子网络。两种盐都表现出部分电荷转移，即rho = 0.5 in 1和非常规rho = 0.4 in2。它们表现为sigma RT = 0.67和33 S cm（-1）且活化能为330和370 K的半导体分别为1和2。与起始电解液的1：3 Cd / SCN比相比，重建后的
• Supramolecular organic conductors based on diiodo-TTFs and spherical halide ion X⁻(X = Cl, Br)
  作者：Tatsuro Imakubo、Takashi Shirahata、Katel Hervé、Lahcène Ouahab

  DOI：10.1039/b512036e

  日期：——

  Novel organic conductors based on four diiodotetrathiafulvalene derivatives, DIET (2-(4,5-diiodo-[1,3]dithiol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine), DIETSe (2-(4,5-diiodo-[1,3]diselenol-2-ylidene)-5,6-dihydro-[1,3]diselenolo[4,5-b][1,4]dithiine), DIEDO (2-(4,5-diiodo-[1,3]dithiol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dioxine) and DIEDO-STF (2-(4,5-diiodo-[1,3]diselenol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dioxine) have been prepared using spherical halide ion X− (X = Cl, Br) as the counter anion. Crystal structure analyses have revealed that all halide salts contain supramolecular structures tailored by the strong I⋯X iodine bond and their molecular arrangement depends on the combination of the group 16 elements included in the donor molecule. The temperature dependence of the electrical resistivity of (DIET)2X(H2O)2 is metallic down to 4.2 K, and they have ideally two-dimensional Fermi surfaces within the donor layer. (DIETSe)2X(CH2Cl2) salts show small temperature dependence of the resistivity down to low temperatures and their “double column” structure is dominated by the Y-shaped architecture composed of the halide ion and the crystalline solvent. On the other hand, (DIEDO)2X and (DIEDO-STF)2X are semiconducting from room temperature. They have another type of “double column” structure, i.e. the adjacent donor molecules along the side-by-side direction are solid-crossing and two types of column are included in the donor layer. The packing motifs of the halide salts based on the oxygen-substituted donor molecules are the same but their electronic states are sensitive to changes in the chalcogen atoms on the inner TTF skeleton.

  X(H2O)2盐的电阻率在4.2 K以下呈金属性，在供体层内具有理想的二维费米表面。(DIETSe)2X(CH2Cl2)盐的电阻率在低温下呈现较小的温度依赖性，其“双柱”结构主要由卤化物离子和结晶溶剂组成的Y形结构主导。另一方面，(DIEDO)2X( )2盐的电阻率在4.2 K以下呈金属性，在供体层内具有理想的二维费米表面。(DIETSe)2X( )盐的电阻率在低温下呈现较小的温度依赖性，其“双柱”结构主要由卤化物离子和结晶溶剂组成的Y形结构主导。
• Syntheses and Properties of Halogenated EDT-TTF Derivatives
  作者：Ulrich Kux、Hironori Suzuki、Shigeru Sasaki、Masahiko Iyoda

  DOI：10.1246/cl.1995.183

  日期：1995.3

  Chlorination and bromination of EDT-TTF produced mainly the dihalogenated products (EDT-TTFCl2 and EDT-TTFBr2) with small amounts of the monohalogenated derivatives. In contrast, iodination of EDT-TTF afforded the monoiodinated derivative as the major product, together with the diiodinated compound. The molecular structures of EDT-TTFCl2 and EDT-TTFBr2 have been determined, and the conductivities of CT-complexes and radical salts of new donors reported here have been measured.

  EDT-TTF的氯化与溴化反应主要生成二卤化产物（EDT-TTFCl2和EDT-TTFBr2），以及少量单卤化衍生物。相比之下，EDT-TTF的碘化反应则主要生成单碘化衍生物，以及二碘化化合物。EDT-TTFCl2和EDT-TTFBr2的分子结构已经确定，本文报道的CT络合物和新型供体自由基盐的导电性也已测定。
• Combining halogen bonding and chirality in a two-dimensional organic metal (EDT-TTF-I2)2(D-camphorsulfonate)·H2O
  作者：Mariya Brezgunova、Kyung-Soon Shin、Pascale Auban-Senzier、Olivier Jeannin、Marc Fourmigué

  DOI：10.1039/c0cc00175a

  日期：——

  A chiral organic conductor with metallic conductivity has been obtained by electrocrystallisation of a diiodotetrathiafulvalene derivative and enantiopure D-camphorsulfonate anion, associated in the solid state by halogen bonding interactions.

  通过二碘四硫富瓦烯衍生物和对映纯D-樟脑磺酸阴离子的电结晶，在固态下通过卤键相互作用，获得了具有金属导电性的手性有机导体。