hexabutoxycarbonyl-1,2,7,8,13,14-tris(tetrathiafulvaleno)-3,4,5,6,9,10,11,12,15,16,17,18-dodecadehydro[18]annulene | 888501-56-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: hexabutoxycarbonyl-1,2,7,8,13,14-tris(tetrathiafulvaleno)-3,4,5,6,9,10,11,12,15,16,17,18-dodecadehydro[18]annulene
• 英文别名: 3,4,5,6,9,10,11,12,15,16,17,18-dodecadehydrotris[bis(butoxycarbonyl)tetrathiafulvaleno][a,g,m][18]annulene；Dibutyl 2-[17,26-bis[4,5-bis(butoxycarbonyl)-1,3-dithiol-2-ylidene]-7,9,16,18,25,27-hexathiatetracyclo[22.3.0.06,10.015,19]heptacosa-1,2,3,4,5,10,11,12,13,14,19,20,21,22,23-pentadecaen-8-ylidene]-1,3-dithiole-4,5-dicarboxylate；dibutyl 2-[17,26-bis[4,5-bis(butoxycarbonyl)-1,3-dithiol-2-ylidene]-7,9,16,18,25,27-hexathiatetracyclo[22.3.0.06,10.015,19]heptacosa-1,2,3,4,5,10,11,12,13,14,19,20,21,22,23-pentadecaen-8-ylidene]-1,3-dithiole-4,5-dicarboxylate
• CAS: 888501-56-2
• 化学式: C₆₀H₅₄O₁₂S₁₂
• 分子量: 1351.87
• InChiKey: SIZQUNGYZSCDHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  84
• 可旋转键数：
  30
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  461
• 氢给体数：
  0
• 氢受体数：
  24

反应信息

• 作为产物：
  描述：

  4',5'-bis(butoxycarbonyl)-4,5-bis(trimethylsilylethynyl)tetrathiafulvalene 在 bis-triphenylphosphine-palladium(II) chloride potassium fluoride 、 copper(l) iodide 、 18-冠醚-6 、 四丁基高氯酸铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 3.5h， 生成 hexabutoxycarbonyl-1,2,7,8,13,14-tris(tetrathiafulvaleno)-3,4,5,6,9,10,11,12,15,16,17,18-dodecadehydro[18]annulene
  参考文献：
  名称：

  三（四硫富瓦烯）十二烷基氢[18]环烯的合成及其自组装。

  摘要：

  [反应：见正文]用钯介导的4,5-二乙炔基-TTFs的三元合成具有酯取代基的电活性三（四硫富瓦烯基）十二烷基氢[18]环戊烯。TTF [18]环烯在溶液中产生堆叠的二聚体，并表现出溶剂致变色和热致变色。TTF [18]环戊烯-六丁酸酯由具有协作SS和pi-pi堆积相互作用的THF水溶液形成分子线。

  DOI：

  10.1021/ol0605530

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。
• Synthesis of Tris(tetrathiafulvaleno)dodecadehydro- [18]annulenes and Their Self-Assembly
  作者：Hideo Enozawa、Masashi Hasegawa、Daikou Takamatsu、Ken-ichi Fukui、Masahiko Iyoda

  DOI：10.1021/ol0605530

  日期：2006.4.1

  [reaction: see text] Synthesis of electroactive tris(tetrathiafulvaleno)dodecadehydro[18]annulenes with ester substituents has been carried out with palladium-mediated cyclotrimerization of 4,5-diethynyl-TTFs. The TTF[18]annulenes produce stacked dimmers in solution and exhibit solvatochromism and thermochromism. The TTF[18]annulene-hexabutyl ester forms a molecular wire from an aqueous THF solution

  [反应：见正文]用钯介导的4,5-二乙炔基-TTFs的三元合成具有酯取代基的电活性三（四硫富瓦烯基）十二烷基氢[18]环戊烯。TTF [18]环烯在溶液中产生堆叠的二聚体，并表现出溶剂致变色和热致变色。TTF [18]环戊烯-六丁酸酯由具有协作SS和pi-pi堆积相互作用的THF水溶液形成分子线。