bis[(4-tert-butylsulfanyl)phenyl]ethyne | 1364344-50-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: bis[(4-tert-butylsulfanyl)phenyl]ethyne
• 英文别名: bis[4-(tert-butylthio)phenyl]acetylene
• CAS: 1364344-50-2
• 化学式: C₂₂H₂₆S₂
• 分子量: 354.58
• InChiKey: GAXJVPYYJYWZOQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.87
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  bis[(4-tert-butylsulfanyl)phenyl]ethyne 、 乙酰氯 在 三溴化硼 作用下， 以 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 反应 3.5h， 以91%的产率得到4,4'-di(acetylthio)tolane
  参考文献：
  名称：

  Correlations between Molecular Structure and Single-Junction Conductance: A Case Study with Oligo(phenylene-ethynylene)-Type Wires

  摘要：

  The charge transport characteristics of 11 tailor-made dithiol-terminated oligo(phenylene-ethynylene) (OPE)-type molecules attached to two gold electrodes were studied at a solid/liquid interface in a combined approach using an STM break junction (STM-BJ) and a mechanically controlled break junction (MCBJ) setup. We designed and characterized 11 structurally distinct dithiol-terminated OPE-type molecules with varied length and HOMO/LUMO energy. Increase of the molecular length and/or of the HOMO-LUMO gap leads to a decrease of the single-junction conductance of the linearly conjugate acenes. The experimental data and simulations suggest a nonresonant tunneling mechanism involving hole transport through the molecular HOMO, with a decay constant beta = 3.4 +/- 0.1 nm(-1) and a contact resistance R-c = 40 k Omega per Au-S bond. The introduction of a cross-conjugated anthraquinone or a dihydroanthracene central unit results in lower conductance values, which are attributed to a destructive quantum interference phenomenon for the former and a broken pi-conjugation for the latter. The statistical analysis of conductance-distance and current-voltage traces revealed details of evolution and breaking of molecular junctions. In particular, we explored the effect of stretching rate and junction stability. We compare our experimental results with DFT calculations using the ab initio code SMEAGOL and discuss how the structure of the molecular wires affects the conductance values.

  DOI：

  10.1021/ja211555x
• 作为产物：
  描述：

  1-溴-4-(叔丁基磺酰基)苯 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 四丁基氟化铵 、 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 反应 21.0h， 生成 bis[(4-tert-butylsulfanyl)phenyl]ethyne
  参考文献：
  名称：

  Correlations between Molecular Structure and Single-Junction Conductance: A Case Study with Oligo(phenylene-ethynylene)-Type Wires

  摘要：

  The charge transport characteristics of 11 tailor-made dithiol-terminated oligo(phenylene-ethynylene) (OPE)-type molecules attached to two gold electrodes were studied at a solid/liquid interface in a combined approach using an STM break junction (STM-BJ) and a mechanically controlled break junction (MCBJ) setup. We designed and characterized 11 structurally distinct dithiol-terminated OPE-type molecules with varied length and HOMO/LUMO energy. Increase of the molecular length and/or of the HOMO-LUMO gap leads to a decrease of the single-junction conductance of the linearly conjugate acenes. The experimental data and simulations suggest a nonresonant tunneling mechanism involving hole transport through the molecular HOMO, with a decay constant beta = 3.4 +/- 0.1 nm(-1) and a contact resistance R-c = 40 k Omega per Au-S bond. The introduction of a cross-conjugated anthraquinone or a dihydroanthracene central unit results in lower conductance values, which are attributed to a destructive quantum interference phenomenon for the former and a broken pi-conjugation for the latter. The statistical analysis of conductance-distance and current-voltage traces revealed details of evolution and breaking of molecular junctions. In particular, we explored the effect of stretching rate and junction stability. We compare our experimental results with DFT calculations using the ab initio code SMEAGOL and discuss how the structure of the molecular wires affects the conductance values.

  DOI：

  10.1021/ja211555x

文献信息

• 1,1′-Dialkynylferrocenes as Substrates for Bidirectional Alkyne Metathesis Reaction
  作者：Jingxiang Ma、Nico Krauße、Holger Butenschön

  DOI：10.1002/ejoc.201500483

  日期：2015.7

  molecular wires, alkyne metathesis was investigated as an alternative to palladium-catalyzed coupling reactions for the synthesis of alkynyl ferrocenes. With a Mortreux catalyst system [Mo(CO)6, 4-chloro- or 2-fluorophenol], (1-propynyl)ferrocenes gave the expected homo metathesis products in moderate yields. Because the Mortreux catalyst system is not compatible with 1,1′-dialkynylferrocenes, a nitridomolybdenum

  在基于二茂铁的分子线的构建中，研究了炔复分解作为钯催化偶联反应的替代方法，用于合成炔基二茂铁。使用 Mortreux 催化剂系统 [Mo(CO)6, 4-氯-或 2-氟苯酚]，（1-丙炔基）二茂铁以中等产率得到预期的均位复分解产物。由于 Mortreux 催化剂体系与 1,1'-二炔基二茂铁不相容，Furstner 引入的氮钼催化剂在双向均和交叉炔复分解反应中进行了测试。尽管以低产率获得均炔复分解产物，但交叉炔复分解反应以良好的总产率提供了预期的产物。