4,5-diiodo-4',5'-ethylenedioxytetrathiafulvalene | 191803-35-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶英
• 英文名称: 4,5-diiodo-4',5'-ethylenedioxytetrathiafulvalene
• 英文别名: 2-(4,5-diiodo-[1,3]dithiol-2-ylidene)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dioxine；2-(4,5-Diiodo-1,3-dithiol-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dioxine
• CAS: 191803-35-7
• 化学式: C₈H₄I₂O₂S₄
• 分子量: 514.192
• InChiKey: ONKHAOQWNRDPKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 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：
  120
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,5-diiodo-4',5'-ethylenedioxytetrathiafulvalene 在 四丁基溴化铵 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Syntheses, Structure and Conducting Properties of Halogenated Ethylenedioxytetrathiafulvalenes

  摘要：

  4,5-Diiodo-, 4,5-dibromo-, and 4,5-dichloro-4',5'-ethylenedioxytetra-thiafulvalenes (EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2) were synthesized in moderate to good yields by the two routes. The first route contains the reaction of EDO-TTF with LDA, followed by quenching with halogenated reagents, and the second route consists of the P(OR)(3)-mediated cross-coupling of 4,5-dihalogenated 1,3-dithiole-2-ones with 4,5-ethylenedioxy-1,3-dithiole-2-thione. The structures of EDO-TTFI2 and EDO-TTFCl2 were determined by X-Ray analysis. The radical-cation salts derived from EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2 show high conductivities, although these compounds contain electron-withdrawing halogens as the substituent.

  DOI：

  10.3987/com-00-s(i)79
• 作为产物：
  描述：

  2-dimethyldithiocarbamyl-1,4-diox-2-ene 在 sodium hydrogensulfide 、 正丁基锂 、 溴 、 二异丙胺 、 lithium bromide 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醇 、 正己烷 、 二氯甲烷 、 溶剂黄146 为溶剂， -78.0~150.0 ℃ 、2.0 kPa 条件下， 反应 15.58h， 生成 4,5-diiodo-4',5'-ethylenedioxytetrathiafulvalene
  参考文献：
  名称：

  Syntheses, Structure and Conducting Properties of Halogenated Ethylenedioxytetrathiafulvalenes

  摘要：

  4,5-Diiodo-, 4,5-dibromo-, and 4,5-dichloro-4',5'-ethylenedioxytetra-thiafulvalenes (EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2) were synthesized in moderate to good yields by the two routes. The first route contains the reaction of EDO-TTF with LDA, followed by quenching with halogenated reagents, and the second route consists of the P(OR)(3)-mediated cross-coupling of 4,5-dihalogenated 1,3-dithiole-2-ones with 4,5-ethylenedioxy-1,3-dithiole-2-thione. The structures of EDO-TTFI2 and EDO-TTFCl2 were determined by X-Ray analysis. The radical-cation salts derived from EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2 show high conductivities, although these compounds contain electron-withdrawing halogens as the substituent.

  DOI：

  10.3987/com-00-s(i)79

文献信息

• 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。
• 4,5-Diiodo-4′,5′-ethylenedioxytetrathiafulvalene and Its Metallic Radical Salts
  作者：Yoshiyuki Kuwatani、Eiji Ogura、Hiroyuki Nishikawa、Isao Ikemoto、Masahiko Iyoda

  DOI：10.1246/cl.1997.817

  日期：1997.8

  4,5-Diiodo-4′,5′-ethylenedioxy-TTF (EDO-TTFI2) was synthesized in moderate yield by the reaction of EDO-TTF with LDA, followed by quenching with CF3(CF2)5I. Although EDO-TTF contains electron-withdrawing iodine as the substituent, this compound has a similar donor ability to BEDT-TTF. The radical-cation salt (EDO-TTFI2)2·ClO4 shows a metallic conductivity down to 50 K, reflecting the strong I···O interaction.

  4,5-二碘-4′,5′-乙二氧基-TTF（EDO-TTFI2）通过EDO-TTF与LDA反应，然后用CF3(CF2)5I淬火，以中等产量合成。虽然EDO-TTF含有作为取代基的吸电子碘，但该化合物具有与BEDT-TTF相似的供体能力。自由基-阳离子盐（EDO-TT ）2·ClO4在50 K时显示出金属导电性，反映了I···O的强相互作用。
• Molecular metals with ferromagnetic interaction between localized magnetic moments
  作者：J. Nishijo、E. Ogura、J. Yamaura、A. Miyazaki、T. Enoki、T. Takano、Y. Kuwatani、M. Iyoda

  DOI：10.1016/s0038-1098(00)00406-3

  日期：2000.11

  Abstract New charge-transfer salts (EDO-TTFI2)2M(mnt)2 (M=Ni,Pt) are the first organic metals with strong ferromagnetic interactions. These salts consist of one-dimensional chains of EDO-TTFI2 donors and M(mnt)2 acceptors aligned in parallel to each other. The metallic conductivity is due to the one dimensional chain of EDO-TTFI2, and a metal–insulator transition occurs at about 90 K. Localized spins

  摘要 新型电荷转移盐 (EDO-TTFI2)2M(mnt)2 (M=Ni,Pt) 是第一种具有强铁磁相互作用的有机金属。这些盐由相互平行排列的 EDO-TT 供体和 M(mnt)2 受体的一维链组成。金属导电性归因于 EDO-TT 的一维链，金属-绝缘体转变发生在大约 90 K。M(mnt)2 的局部自旋表现为一维铁磁体，与传导电子相互作用。铁磁相互作用的起源是 M(mnt)2 分子轨道的正交性和自旋极化效应，这是由麦康奈尔的第一个模型解释的。