4',5'-bis(butylthio)-4-iodotetrathiafulvalene | 717918-81-5

• 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'-bis(butylthio)-4-iodotetrathiafulvalene
• 英文别名: 4,5-bis(butylthio)-4'-iodotetrathiafulvalene；4,5-Bis(butylsulfanyl)-2-(4-iodo-1,3-dithiol-2-ylidene)-1,3-dithiole
• CAS: 717918-81-5
• 化学式: C₁₄H₁₉IS₆
• 分子量: 506.605
• InChiKey: DDWSIZNWVYTHJM-UHFFFAOYSA-N

物化性质

• 沸点：
  445.6±45.0 °C(Predicted)
• 密度：
  1.66±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  4',5'-bis(butylthio)-4-iodotetrathiafulvalene 在 四(三苯基膦)钯 copper(l) iodide 、 正丁基锂 作用下， 生成 2-[4,5-Bis(butylsulfanyl)-1,3-dithiol-2-ylidene]-4-[2-[2-[4,5-bis(butylsulfanyl)-1,3-dithiol-2-ylidene]-5-iodo-1,3-dithiol-4-yl]ethynyl]-5-iodo-1,3-dithiole
  参考文献：
  名称：

  Mono- and bis(tetrathiafulvaleno)hexadehydro[12]annulenesElectronic supplementary information (ESI) available: cyclic voltammograms of the annulenes 1 and 2. See http://www.rsc.org/suppdata/cc/b4/b407200f/

  摘要：

  我们合成了具有一个或两个 TTF 单元的六氢[12]琥珀烯，以研究其基于 TTF 和[12]琥珀烯分子的 π 两性特性；这些化合物显示出多重氧化还原电位、溶解变色和形成大型夹层复合物。

  DOI：

  10.1039/b407200f
• 作为产物：
  描述：

  4,5-bis(butylthio)-1,3-dithiole-2-thione 在 正丁基锂 、 lithium hydroxide monohydrate 、 亚磷酸三乙酯 作用下， 以 N-甲基吡咯烷酮 为溶剂， 生成 4',5'-bis(butylthio)-4-iodotetrathiafulvalene
  参考文献：
  名称：

  Self-Assembly of Radially π-Extended Tetrathiafulvalene Tetramers for Visible and Near Infrared Electrochromic Nanofiber

  摘要：

  研究了锚定在 1,2,4,5- 四炔基苯上的径向 π 延伸的四噻吩富戊二烯（TTF）四元分子的自组装和电致变色纳米纤维的形成。带有 SBu 取代基的四聚体在溶液中进行了自组装。通过与 Fe(ClO4)3 化学氧化得到的阳离子四聚体在溶液中表现出明显的电致色性。它们的电子光谱显示了与分子间混合价聚集（TTF//TTF）-+ 和π聚集（TTF-+//TTF-+）相对应的吸收带，这是由于阳离子物种中的分子关联性很强。此外，四聚体还从 CHCl3-hexane 中形成了缠结的纳米级纤维材料。纳米纤维在氧化铟锡电极上的电化学氧化显示了可重复的氧化还原曲线。纳米纤维显示出显著的电致变色行为：纤维的颜色从紫色（中性）变为棕/棕绿色（二阳离子和三阳离子）和绿色（四阳离子）。纳米纤维的这些颜色变化与溶液中的颜色变化相似，氧化纳米纤维的电子能谱反映了阳离子纳米纤维中堆叠的 TTF 单元。

  DOI：

  10.1246/bcsj.20190283

文献信息

• Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores
  作者：Huixin Jiang、Virginia Mazzanti、Christian R Parker、Søren Lindbæk Broman、Jens Heide Wallberg、Karol Lušpai、Adam Brincko、Henrik G Kjaergaard、Anders Kadziola、Peter Rapta、Ole Hammerich、Mogens Brøndsted Nielsen

  DOI：10.3762/bjoc.11.104

  日期：——

  A selection of cyclic and acyclic acetylenic scaffolds bearing two tetrathiafulvalene (TTF) units was prepared by different metal-catalyzed coupling reactions. The bridge separating the two TTF units was systematically changed from linearly conjugated ethyne, butadiyne and tetraethynylethene (trans-substituted) units to a cross-conjugated tetraethynylethene unit, placed in either acyclic or cyclic

  通过不同的金属催化偶联反应，制备了带有两个四硫富瓦烯（TTF）单元的环状和非环状炔基骨架。分隔两个TTF单元的桥系统地从线性共轭乙炔，丁二炔和四乙炔基乙烯（反式取代）单元改为交叉共轭四乙炔基乙烯单元（以无环或环状排列方式放置）。环状结构对应于具有环内和环外双键的所谓的拉丹环。通过循环伏安法，紫外可见近红外光谱和EPR吸收光谱法研究了这些分子中两个氧化还原活性TTF单元之间的相互作用。还电化学研究了炔属核的电子接受性能。
• Metal cation binding to acetylenic tetrathiafulvalene–pyridine conjugates: affinity tuned by preorganization and cavity size
  作者：Søren Lindbæk Broman、Cecilie Lindholm Andersen、Martyn Jevric、Christian Gregers Tortzen、Ole Hammerich、Mogens Brøndsted Nielsen

  DOI：10.1016/j.tet.2016.08.001

  日期：2016.9

  A series of three structurally related mono-, bidentate and macrocyclic TTF-pyridine hosts were prepared and titrated with several metal cations including Ag+ and Pb2+ and studied using NMR- and UV-vis spectroscopy and cyclic voltammetry. For Ag+, we found an eightfold increase in binding affinity between the bidentate and macrocyclic host and conversely, for Pb2+, a 100-fold drop. Density functional theory (DFT) calculations support the increased binding affinity for Ag+ is due to an N...N distance for the uncomplexed macrocycle very much suited for binding of Ag+ but being too small for Pb2+. The bidentate host, on the other hand, is of a suitable size for Pb2+. (C) 2016 Elsevier Ltd. All rights reserved.
• Synthesis and Properties of Thienylene-Ethynylene-Tetrathiafulvalene Oligomers
  作者：Masashi Hasegawa、Kenji Hara、Ken-ichi Tokuyama、Masahiko Iyoda

  DOI：10.1080/10426501003773381

  日期：2010.5.27

  A series of thienylene-ethynylene-tetrathiafulvalene oligomers 1-6 have been synthesized by the Sonogashira reaction of iodo-tetrathiafulvalene derivatives with thienylethynes. The X-ray structure of 4,5-bis(2-thienylethynyl)tetrathiafulvalene (1b) revealed a planar structure of the molecule. The electronic spectra of neutral oligomers 1-6 suggest a partial intramolecular charge transfer between the TTF and thienylethyne units. The cyclic voltammetric measurements of 1-4 showed multi-redox processes.
• Synthesis and Electrochromic Properties of Bis(2-tetrathiafulvalenylethynylphenyl)ethynes
  作者：Masahiko Iyoda、Masashi Hasegawa、Yusuke Kobayashi、Kenji Hara、Hideo Enozawa

  DOI：10.3987/com-08-s(f)106

  日期：——

  Bis(2-tetrathiafulvalenylethynylphenyl)ethynes 1a and 1b have been synthesized by the Sonogashira coupling reaction of 4-iodotetrathiafulvalenes with bis(2-ethynylphenyl)ethyne. The dimeric TTFs 1a and 1b form an open-chain anti conformation in the neutral and tetracation states, whereas la and 1b form a helical syn conformation in the mono- and dication states owing to their face-to-face interaction between the two TTF units. Such conformational changes lead to unique electrochromic and on-off switching properties of 1a and 1b in UV-vis-NIR spectra.
• The Gilded Edge in Acetylenic Scaffolding: Pd-Catalyzed Cross-Coupling Reactions of Phosphine–Gold(I) Oligoynyl Complexes
  作者：Virginia Mazzanti、Huixin Jiang、Henrik Gotfredsen、Thorbjørn J. Morsing、Christian R. Parker、Mogens Brøndsted Nielsen

  DOI：10.1021/ol5015587

  日期：2014.7.18

  Stable bis(gold(I) alkynyl) complexes of tetraethynylethene (TEE) derivatives were readily prepared and employed in Sonogashira-like palladium-catalyzed phosphine-gold(I) halide elimination reactions with aryl iodides and redox-active tetrathiafulvalene (TTF) mono- and bisiodides. This presents a particularly convenient method for the preparation of symmetrical and asymmetrical tetrathiafulvalene (TTF)-fused radiaannulenes in good yields.