4,5-diiodo-[1,3]dithiole-2-one | 163525-49-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 4,5-diiodo-[1,3]dithiole-2-one
• 英文别名: 4,5-diiodo-1,3-dithiole-2-one；4,5-diiodo-2-oxo-1,3-dithiole；4,5-Diiodo-1,3-dithiol-2-one
• CAS: 163525-49-3
• 化学式: C₃I₂OS₂
• 分子量: 369.973
• InChiKey: ZVKUMKMJZIUTDC-UHFFFAOYSA-N

物化性质

• 沸点：
  302.8±52.0 °C(Predicted)
• 密度：
  3.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,5-diiodo-[1,3]dithiole-2-one 在 亚磷酸三乙酯 作用下， 生成 tetraiodotetrathiafulvalene
  参考文献：
  名称：

  Gompper, Rudolf; Hansel, Jan-Gerd; Hock, Joachim, Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 96, # 1-4, p. 521 - 526

  摘要：

  DOI：
• 作为产物：
  描述：

  4,5-diiodo-[1,3]dithiole-2-thione 在 mercury(II) diacetate 、 溶剂黄146 作用下， 以 氯仿 为溶剂， 反应 2.0h， 以68%的产率得到4,5-diiodo-[1,3]dithiole-2-one
  参考文献：
  名称：

  Hal⋯Hal interactions in a series of three isostructural salts of halogenated tetrathiafulvalenes. Contribution of the halogen atoms to the HOMO–HOMO overlap interactions

  摘要：

  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。

  DOI：

  10.1039/b100103p

文献信息

• Self-Assembly, Chromic Properties, and Nanostructure Formation of Tetrathiafulvalene-Fused Dodecadehydro[18]annulenes
  作者：Hideo Enozawa、Takeshi Takahashi、Tohru Nishinaga、Tadashi Kato、Masashi Hasegawa、Masahiko Iyoda

  DOI：10.1246/bcsj.20120135

  日期：2012.10.15

  Multifunctional dodecadehydrotris(tetrathiafulvaleno)[18]annulenes 1b–1d, which have six peripheral butylthio substituents or six ester substituents, were synthesized together with the corresponding [12]annulene 2c. The [18]annulenes 1b–1d easily formed stacked dimers and higher oligomers in solution via nanoscopic phase separation among the π-frame, ester or alkylthio substituents, and inner sphere to show solvatochromism and thermochromism. Furthermore, the strong self-aggregation of their oxidized radical cations in solution resulted in electrochromism depending on the formation of various types of mixed-valence states and π-dimers. Interestingly, self-aggregation of the [18]annulenes 1b–1d in amphiphilic media such as THF–H2O either produced fibrous structures in the case of the hexabutylthio derivative 1b and hexabutyl ester 1c or resulted in the temperature hysteresis of the color, UV–vis absorptions, and 1H NMR signals obtained in solution in the case of the hexaoctyl ester 1d which forms no fiber and precipitate under similar conditions. It is noted that fibers of the hexabutyl ester 1c can be aligned in a magnetic field using the large diamagnetic response of the [18]annulene frame for the driving force. A small difference in the substituents of 1b–1d causes a remarkable change in either their solvato- and electrochromism or nanostructure formation of 1b–1d based on the self-assembling nature both in solution and in the solid state.

  多功能十二氢三（四硫富戊烯）[18]琥珀烯 1b-1d 与相应的[12]琥珀烯 2c 一起合成，[18]琥珀烯 1b-1d 具有六个外围丁硫基或六个酯基取代基。[18]琥珀烯 1b-1d 在溶液中很容易通过π-框架、酯或烷硫基取代基和内球之间的纳米相分离形成叠层二聚体和更高的低聚物，从而显示出溶解色度和热色度。此外，它们的氧化基阳离子在溶液中的强烈自聚集导致了电致色性，这取决于各种混合价态和 π 二聚体的形成。有趣的是，[18]琥珀烯 1b-1d 在 THF-H2O 等两亲介质中的自聚，要么在六丁基硫代衍生物 1b 和六丁基酯 1c 中产生纤维结构，要么导致在溶液中获得的颜色、紫外可见吸收和 1H NMR 信号的温度滞后，而六辛基酯 1d 在类似条件下不会形成纤维和沉淀。值得注意的是，利用[18]环烯框架的大二磁性响应作为驱动力，六丁酯 1c 的纤维可以在磁场中排列。基于 1b-1d 在溶液和固态中的自组装性质，1b-1d 取代基的微小差异都会导致其溶解性和电致色性发生显著变化，或导致 1b-1d 纳米结构的形成。
• Bis(tetrathiafulvaleno)octadehydro[20]annulene with Multi-functionality
  作者：Masahiko Iyoda、Hideo Enozawa、Yoshihiro Miyake

  DOI：10.1246/cl.2004.1098

  日期：2004.9

  Sulfur-bridged octadehydro[20]annulene 1c annelated with two TTF rings was synthesized and its multi-functional properties were ascertained. The annulene exhibits paratropicity, solvatochromism, electrochromism and multi-redox potentials in solution, and its cation radical in the solid state shows self-association and electric conductivity.

  合成了带有两个 TTF 环的硫桥八氢[20]琥珀烯 1c，并确定了其多功能特性。该琥珀烯在溶液中表现出副向性、溶解变色性、电变色性和多重氧化还原电位，其阳离子基在固态中表现出自结合和导电性。
• Azulene-substituted TTF derivatives
  作者：Hiroshi M. Yamamoto、Jun-ichi Yamaura、Reizo Kato

  DOI：10.1039/a703737f

  日期：——

  In order to examine Little’s model for organic superconductors, several azulene-substituted TTF derivatives were synthesized. Measurements of the oxidation potentials using cyclic voltammetry (CV) provide their donor abilities. The molecular structure of AET (azulenoethylenedithiotetrathiafulvalene) was determined by X-ray analysis. Cation radical salts of synthesized donors with BF4– , ClO4– , PF6– , AsF6– and [Pt(dmit)2 ]n–(dmit=C3S52–=2-thioxo-1,3-dithiole-4,5-dithiolate) were prepared by galvanostatic electrolyses. Temperature-dependent electrical resistances indicate that these salts are all semiconductive. The crystal structure of (AET)2 [Pt(dmit)2 ] was determined by X-ray analysis and its electronic structure is discussed.

  为了研究LiTTle的有机超导体模型，我们合成了几种取代了苊的TTF衍生物。通过循环伏安法（CV）测量氧化电位，从而确定它们的供体能力。通过X射线分析确定了AET（苊基乙撑二硫代四硫富瓦烯）的分子结构。通过恒电流电解法，我们制备了合成供体的阳离子自由基盐，其中BF4–、ClO4–、PF6–、AsF6–和[Pt(dmit)2]n–（dmit=C3S52–=2-硫酮-1,3-二硫杂环戊烯-4,5-二硫醇酸根）的阳离子自由基盐。温度相关的电阻表明这些盐都是半导体的。通过X射线分析确定了（AET）2[Pt（dmit）2]的晶体结构，并讨论了其电子结构。
• 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。
• Solvent dependence of crystal morphology, donor/anion ratio and electrical conductivity in a series of hexagonal supramolecular organic conductors based on diiodo(pyrazino)tetrathiafulvalene (DIP)
  作者：Tatsuro Imakubo、Ryosuke Murayama

  DOI：10.1039/c2ce26739j

  日期：——

  A series of hexagonal supramolecular organic conductors has been tailored by the iodine bond based on the selenium-free π-donor and halogen-free solvent. The solvent dependence of crystal morphology, donor/anion ratio and electrical conductivity was investigated together with characteristic recyclability of the neutral donor molecule.

  基于不含硒的π供体和不含卤素的溶剂，通过碘键定制了一系列六角形的超分子有机导体。研究了溶剂对晶体形态，供体/阴离子比和电导率的依赖性以及中性供体分子的可回收性。