5-thiohexyl-(3,4-ethylenedioxy)thiophene | 1202878-12-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 5-thiohexyl-(3,4-ethylenedioxy)thiophene
• 英文别名: 2-(hexylthio)-3,4-ethylenedioxythiophene；5-Hexylsulfanyl-2,3-dihydrothieno[3,4-b][1,4]dioxine；5-hexylsulfanyl-2,3-dihydrothieno[3,4-b][1,4]dioxine
• CAS: 1202878-12-3
• 化学式: C₁₂H₁₈O₂S₂
• 分子量: 258.406
• InChiKey: KAABQSROPXZWCZ-UHFFFAOYSA-N

物化性质

• 沸点：
  347.2±42.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  72
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-thiohexyl-(3,4-ethylenedioxy)thiophene 在 四(三苯基膦)钯 、 正丁基锂 、 甲基溴化镁 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 18.0h， 生成 1-(4-(5-thiohexyl-(3,4-ethylenedioxythiophen-2-yl))pyridine-2-yl)ethanone
  参考文献：
  名称：

  Diastereoisomers of Ruthenium Dyes with Unsymmetric Ligands for DSC: Fundamental Chemistry and Photovoltaic Performance

  摘要：

  A new thiocyanic acid-free ruthenium sensitizer, CYC-B29, containing two unsymmetrical ancillary ligands, was synthesized, and its three diastereoisomers CYC-B29-CC, CYC-B29-TT, and CYC-B29-CT with significantly different optical, electronic, and electrochemical properties were carefully separated. CYC-B29-TT with the smallest size has the strongest absorption coefficient of the MLCT band, the shortest gimel(max), the lowest highest occupied molecular orbital level and the highest dye loading. Therefore, dye-sensitized solar cell based on CYC-B29-TT has the highest efficiency, which is two times higher than that of CYC-B29-CC-sensitized device and 10% higher than that of N719-based cell. Time-dependent density functional theory-calculated transition bands for the three isomers are not identical, and only CYC-B29-TT has the calculated transition bands close to the experimental absorption profile. Although the calculated transition bands for CYC-B29-CC and CYC-B29-CT are not consistent with the experimental data, the ground-state vertical excitation energy with oscillator strength and electron-density difference map data combining with the dye loading predict correctly the order of the photocurrent for the three isomers sensitized devices.

  DOI：

  10.1021/acs.inorgchem.5b01967
• 作为产物：
  描述：

  溴己烷 、 3,4-乙烯二氧噻吩 在 正丁基锂 、 sulfur 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以80%的产率得到5-thiohexyl-(3,4-ethylenedioxy)thiophene
  参考文献：
  名称：

  CF 3取代基对高效环化金属钌敏化剂电荷转移动力学的影响

  摘要：

  合成了六种无硫氰酸盐的配合物DUY1-DUY6，并研究了它们在染料敏化太阳能电池中的应用，以研究位于辅助配体中的CF 3取代基和锚定配体的结构对理化性质的影响。钌敏化剂的电荷转移动力学和光电性质。当将吸电子基团安装在环金属化配体上并扩展了其与辅助配体的π共轭时，钌配合物的前沿轨道能级似乎足以进行有效的电子注入和染料再生，同时具有较高的采光能力。两个吸电子CF 3相对于o -CF 3和p -CF 3基，亚甲基到环金属化位置降低了金属中心的电子密度。含有m -CF 3基团的敏化剂还显示出更有利的β最低空位自旋轨道分布，以促进氧化染料与碘离子之间的相互作用，从而促进染料的再生。与在N，N-二甲基甲酰胺溶液中吸收的TiO 2膜相比，DUY1-DUY4的吸收曲线吸收了更长的波长，尤其是λY最大的DUY1和DUY2染料。红移最高达30 nm。DUY2染色电池的效率最高，为9.03％，而DUY1，DUY

  DOI：

  10.1021/acs.inorgchem.6b02088

文献信息

• Theory-Driven Spectral Control of Bis-EDOT Arylene Radical Cation Chromophores
  作者：Linda Nhon、Simone L. Tennyson、Mason W. Butt、John Bacsa、Aimée L. Tomlinson、John R. Reynolds

  DOI：10.1021/acs.chemmater.2c02054

  日期：2022.11.8

  are performed to understand the evolution of the geometric, optical, and electronic properties as the neutral trimers are converted to the radical cation, and to some extent, the dication state. We find that changes in geometric conformation in the radical cations as a result of methoxy substituents are reflected in changes in the dominant high-energy absorbance peak that are associated mainly with the

  π-共轭材料的电子结构是其独特的光电特性的原因，并且可以通过引入具有不同空间或电子相互作用的取代基来控制扭转扭曲、非共价静电相互作用和电子丰富程度。控制中性共轭分子的电子跃迁的结构-性质关系已被很好地理解，但对于相应的自由基阳离子/阴离子，这种相同的关系几乎没有受到关注，而且可观察到的跃迁可能难以先验地预测。在这里，我们使用量子计算，特别是密度泛函理论 (DFT) 和时间相关 DFT (TD-DFT)，预测功能性取代基在二氧噻吩基三杂环上的选择和位置如何影响相应自由基阳离子和双阳离子态的光学性质。具体来说，我们检查了七种硫代烷基取代的双（3,4-亚乙基二氧噻吩）-1,4-亚苯基（BEDOT-B ) 分子在中心亚苯基周围具有不同的烷氧基，并通过 TD-DFT 比较了它们的光电、几何和激发态特性。然后，我们使用三种模型化合物 BEDOT-苯(BEDOT-B)、BEDOT-甲氧基亚苯基 ( BEDOT-MOB
• Rigid oligomers based on the combination of 3,6-dimethoxythieno[3,2-b]thiophene and 3,4-ethylenedioxythiophene
  作者：Mathieu Turbiez、Noémie Hergué、Philippe Leriche、Pierre Frère

  DOI：10.1016/j.tetlet.2009.10.021

  日期：2009.12

  New oligomers based on the combination of the 3,6-dimethoxythieno[3,2-b]thiophene and 3,4-ethylenedioxythiophene (EDOT) moieties have been prepared and studied by UV-vis spectroscopy and cyclic voltammetry. The use of the intrinsically rigid thienothiophene units in addition to the S center dot center dot center dot O intramolecular interactions leads to planar conformation of the conjugated chains. While the radical cations of oligomers end capped by n-hexyl chains show a tendency to the dimerization, those substituted by n-hexylsulfanyl chains present a high stability. (c) 2009 Elsevier Ltd. All rights reserved.
• Diastereoisomers of Ruthenium Dyes with Unsymmetric Ligands for DSC: Fundamental Chemistry and Photovoltaic Performance
  作者：Jheng-Ying Li、Chia Lee、Chia-Yuan Chen、Wen-Long Lee、Ren Ma、Chun-Guey Wu

  DOI：10.1021/acs.inorgchem.5b01967

  日期：2015.11.2

  A new thiocyanic acid-free ruthenium sensitizer, CYC-B29, containing two unsymmetrical ancillary ligands, was synthesized, and its three diastereoisomers CYC-B29-CC, CYC-B29-TT, and CYC-B29-CT with significantly different optical, electronic, and electrochemical properties were carefully separated. CYC-B29-TT with the smallest size has the strongest absorption coefficient of the MLCT band, the shortest gimel(max), the lowest highest occupied molecular orbital level and the highest dye loading. Therefore, dye-sensitized solar cell based on CYC-B29-TT has the highest efficiency, which is two times higher than that of CYC-B29-CC-sensitized device and 10% higher than that of N719-based cell. Time-dependent density functional theory-calculated transition bands for the three isomers are not identical, and only CYC-B29-TT has the calculated transition bands close to the experimental absorption profile. Although the calculated transition bands for CYC-B29-CC and CYC-B29-CT are not consistent with the experimental data, the ground-state vertical excitation energy with oscillator strength and electron-density difference map data combining with the dye loading predict correctly the order of the photocurrent for the three isomers sensitized devices.
• Effect of the CF₃ Substituents on the Charge-Transfer Kinetics of High-Efficiency Cyclometalated Ruthenium Sensitizers
  作者：The-Duy Nguyen、Chun-Han Lin、Chun-Guey Wu

  DOI：10.1021/acs.inorgchem.6b02088

  日期：2017.1.3

  dye-sensitized solar cell was studied to explore the effect of the CF3 substituent positioned in the ancillary ligand and the structure of the anchoring ligand on the physicochemical properties, charge-transfer kinetics, and photovoltaic properties of ruthenium sensitizers. When the electron-withdrawing groups were installed on the cyclometalating ligands and their π conjugation of the ancillary ligand was extended

  合成了六种无硫氰酸盐的配合物DUY1-DUY6，并研究了它们在染料敏化太阳能电池中的应用，以研究位于辅助配体中的CF 3取代基和锚定配体的结构对理化性质的影响。钌敏化剂的电荷转移动力学和光电性质。当将吸电子基团安装在环金属化配体上并扩展了其与辅助配体的π共轭时，钌配合物的前沿轨道能级似乎足以进行有效的电子注入和染料再生，同时具有较高的采光能力。两个吸电子CF 3相对于o -CF 3和p -CF 3基，亚甲基到环金属化位置降低了金属中心的电子密度。含有m -CF 3基团的敏化剂还显示出更有利的β最低空位自旋轨道分布，以促进氧化染料与碘离子之间的相互作用，从而促进染料的再生。与在N，N-二甲基甲酰胺溶液中吸收的TiO 2膜相比，DUY1-DUY4的吸收曲线吸收了更长的波长，尤其是λY最大的DUY1和DUY2染料。红移最高达30 nm。DUY2染色电池的效率最高，为9.03％，而DUY1，DUY