(E)-4,5,4',5'-Tetrahydro-[6,6']bi[cyclopenta[b]thiophenylidene] | 302906-75-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (E)-4,5,4',5'-Tetrahydro-[6,6']bi[cyclopenta[b]thiophenylidene]
• 英文别名: (6E)-6-(4,5-dihydrocyclopenta[b]thiophen-6-ylidene)-4,5-dihydrocyclopenta[b]thiophene
• CAS: 302906-75-8
• 化学式: C₁₄H₁₂S₂
• 分子量: 244.381
• InChiKey: FGVDFHVPWIENEI-VAWYXSNFSA-N

物化性质

• 沸点：
  391.3±37.0 °C(Predicted)
• 密度：
  1.365±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-4,5,4',5'-Tetrahydro-[6,6']bi[cyclopenta[b]thiophenylidene] 在 potassium tert-butylate 、 三氯氧磷 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 生成 (E)-2-formyl-2'-2-[(E)-(4-N,N-dihexylaminobenzylidene)methyl]-6,6'-bis(4,5-dihydro-6H-cyclopenta[b]thienylidene)
  参考文献：
  名称：

  Huge enhancement of the quadratic nonlinear optical susceptibility in push–pull chromophores based on bridged dithienylethylene spacers

  摘要：

  在推拉式 NLO 荧光中，用其桥接类似物取代开链二噻吩乙烯Ï-共轭间隔物，可显著提高二次超极性。

  DOI：

  10.1039/b001700k
• 作为产物：
  描述：

  反-3-(3-噻吩基)丙烯酸 在 sodium amalgam 、 三氯化铝 、 氯化亚砜 、 水 、 四氯化钛 、 锌 作用下， 以 四氢呋喃 、 二硫化碳 为溶剂， 生成 (E)-4,5,4',5'-Tetrahydro-[6,6']bi[cyclopenta[b]thiophenylidene]
  参考文献：
  名称：

  通过π共轭体系的刚性控制导电聚合物的带隙

  摘要：

  的硬化Ë通过与中央双键引线噻吩环桥接到一个-1,2-（2,2'- dithienylethylene）约 所得导电聚合物的带隙降低0.40 eV。

  DOI：

  10.1039/c39940002249

文献信息

• Design and Synthesis of Push−Pull Chromophores for Second-Order Nonlinear Optics Derived from Rigidified Thiophene-Based π-Conjugating Spacers
  作者：Jean-Manuel Raimundo、Philippe Blanchard、Nuria Gallego-Planas、Nicolas Mercier、Isabelle Ledoux-Rak、Rolland Hierle、Jean Roncali

  DOI：10.1021/jo010713f

  日期：2002.1.1

  Two series of push-pull chromophores built around thiophene-based pi-conjugating spacers rigidified either by covalent bonds or by noncovalent intramolecular interactions have been synthesized and characterized by UV-vis spectroscopy, electric field induced second harmonic generation (EFISH) and differential scanning calorimetry. Comparison of the linear and second-order nonlinear optical properties

  合成了两个系列的推挽生色团，它们围绕通过共价键或通过非共价分子内相互作用而硬化的基于噻吩的pi共轭间隔基构建，并通过紫外可见光谱，电场诱导的二次谐波产生（EFISH）和差示扫描量热法进行了表征。基于共价桥联二噻吩基乙烯（DTE）间隔基的发色团与基于开链DTE的类似物的生色团的线性和二阶非线性光学性质的比较表明，间隔基的刚性共同导致吸收最大值的显着红移分子二次超极化率（mu beta）大大提高，达到了迄今为​​止报道的最高值。NLO-phores的第二系列是从2,2' -双（3,4-乙撑二氧噻吩）（BEDOT）π共轭间隔基。如X射线和UV-vis数据所示，在这种情况下，间隔物的刚性源自硫和氧原子之间的非共价分子内相互作用。再次，与基于未取代的联噻吩间隔基的母体化合物的比较揭示了最大吸收的显着红移和μβ的大大增强。为了区分乙二氧基的电子和几何效应的贡献，已经合成了基于3，4-乙二氧基噻吩（ED
• Organic and inorganic photosensitizer dyes
  申请人：Wu Chun-Guey

  公开号：US20110288300A1

  公开（公告）日：2011-11-24

  The present invention discloses organic and inorganic photosensitizer dyes as the following formulas (1) to (3), wherein the substituents “A, B, D and G” are as defined in claim 1 .

  本发明公开了有机和无机光敏染料，其化学式如下（1）至（3），其中取代基“A、B、D和G”如权利要求1中所定义。
• Fine Tuning of the Electronic Properties of Linear π-Conjugated Oligomers by Covalent Bridging
  作者：Philippe Blanchard、Patrick Verlhac、Laurent Michaux、Pierre Frère、Jean Roncali

  DOI：10.1002/chem.200500853

  日期：2006.1.23

  that the sites of fixation of the bridges on the pi-conjugated backbone exert a determining effect on the relative stability of the cation radical and dication. Examination of these various results in the light of theoretical calculations shows that in addition to a local control of bond length alternation, and hence of the HOMO-LUMO gap, the fixation of covalent bridges at selected positions of the pi-conjugated

  已经通过多步合成方法构建了一系列的低聚噻吩亚乙烯基，即通过连接在共轭主链的不同位置的乙烯桥而刚性化的π-共轭低聚物。电子吸收光谱显示，与开链参考化合物的光谱相比，共轭体系的刚性产生最大吸收的红移和HOMO-LUMO能隙的缩小。所有低聚物的循环伏安图显示，这些化合物可被可逆地氧化成其阳离子自由基和阳离子，而刚性化作用则使第一氧化电位产生较大的负移，这表明HOMO含量显着增加。电化学数据证实，共价桥接强烈影响HOMO和LUMO的水平，这些数据表明，在pi共轭骨架上的桥固定位点对阳离子自由基和离子的相对稳定性起决定性作用。根据理论计算检查这些各种结果表明，除了局部控制键长交替以及HOMO-LUMO间隙外，共价桥固定在π共轭体系的选定位置还限制了变形。 π共轭结构在氧化成带电态时的结构。
• Linearly extended hybrid tetrathiafulvalene analogues with bridged dithienylethyleneπ-conjugating spacers
  作者：Hugues Brisset、Soazig Le Moustarder、Philippe Blanchard、Bertrand Illien、Amédée Riou、Jesus Orduna、Javier Garin、Jean Roncali

  DOI：10.1039/a701463e

  日期：——

  New linearly extended π-electron donors based on bridged dithienylethylene (DTE) end-capped with diversely substituted 1,3-dithiol-2-ylidene electron-releasing groups have been synthesized by Wittig–Horner olefination of appropriate aldehydes. Cyclic voltammetry shows that whereas the unbridged analogues are directly oxidized to the dication state through a two-electron transfer, rigidification of the DTE spacer leads to the splitting of the two-electron wave into two successive one-electron steps due to the decrease of the potential corresponding to the formation of the cation radical. This unusual electrochemical behaviour is interpreted with the help of theoretical calculations which suggest that these effects are related to the enhanced electron delocalization resulting from the rigidification of the DTE spacer. This conclusion is supported by an X-ray diffraction structural analysis which reveals that in addition to a fully planar conformation stabilized by intramolecular S‥S interactions, the bridging of the DTE spacer leads to a significant reduction of bond length alternation.

  通过对适当的醛进行 WittigâHorner 烯化反应，合成了以桥接的二噻吩乙烯（DTE）为基础、以多种取代的 1,3-二硫醇-2-亚基电子释放基团为端盖的新型线性延伸 Ï 电子供体。循环伏安法显示，未桥接的类似物通过双电子转移直接氧化成二阳离子状态，而 DTE 间隔的刚性化会导致双电子波分裂成两个连续的单电子步骤，这是因为阳离子自由基的形成导致电位下降。理论计算表明，这些效应与 DTE 隔层刚性化导致的电子析出增强有关，从而解释了这种不寻常的电化学行为。这一结论得到了 X 射线衍射结构分析的支持，该分析表明，除了分子内 Sâ¥S 相互作用稳定的完全平面构象外，DTE 间隔物的桥接还导致键长交替的显著减少。
• Bridged Dithienylethylenes as Precursors of Small Bandgap Electrogenerated Conjugated Polymers
  作者：Philippe Blanchard、Hugues Brisset、Bertrand Illien、Amédée Riou、Jean Roncali

  DOI：10.1021/jo9623447

  日期：1997.4.1

  Bridged dithienylethylenes (DTEs) bearing solubilizing alkyl chains at various positions (2-5) have been synthesized by McMurry dimerization of cyclopenta[b]thiophen-6-ones. In order to introduce alkyl substituents at different positions of the DTE molecule, the precursor ketones have been prepared by different strategies based on a combination of Mannich or Wittig-Horner reaction and Friedel-Craft intramolecular cyclization. The position and the length of the alkyl substituents exert a strong effect on the ability of the precursor to undergo electrochemical polymerization. Thus, whereas substitution at the alpha-position of the ethylene linkage (3) results in a rapid inhibition of electropolymerization, introduction of alkyl chains at the beta-position (4, 5) greatly improves the efficiency of the polymerization process. The analysis of the electrochemical and optical properties of the polymers shows that rigidification of the DTE molecule leads to a significant decrease of the oxidation potential and bandgap. A comparative analysis of DTE and its bridged analogues by means of X-ray diffraction reveals, in agreement with experimental and theoretical results, that the observed reduction of both the HOMO-LUMO gap of the precursor and the bandgap of the corresponding polymers are related to a relaxation of bond length alternation in the DTE moiety.