((4-(tert-butylthio)phenyl)ethynyl)triisopropylsilane | 795274-48-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: ((4-(tert-butylthio)phenyl)ethynyl)triisopropylsilane
• 英文别名: 2-(4-Tert-butylsulfanylphenyl)ethynyl-tri(propan-2-yl)silane
• CAS: 795274-48-5
• 化学式: C₂₁H₃₄SSi
• 分子量: 346.652
• InChiKey: DJALFZZWGQLRME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.15
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ((4-(tert-butylthio)phenyl)ethynyl)triisopropylsilane 在 四丁基氟化铵 、 溴 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 acetylsulfanyl-4-(ethynyl)benzene
  参考文献：
  名称：

  Bromine catalyzed conversion of S-tert-butyl groups into versatile and, for self-assembly processes accessible, acetyl-protected thiols

  摘要：

  在乙酰氯和乙酸存在的情况下，通过催化溴的用量，将叔丁基保护基团简便高效地转化为硫醇的乙酰基保护基团。这种相当温和的反应条件对于硫官能化目标结构的新保护基策略具有特别重要的意义。

  DOI：

  10.1039/b408677e
• 作为产物：
  描述：

  1-溴-4-(叔丁基磺酰基)苯 、 三异丙基硅基乙炔 在 copper(l) iodide 、 trans-bis(triphenylphosphine)palladium dichloride 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以89%的产率得到((4-(tert-butylthio)phenyl)ethynyl)triisopropylsilane
  参考文献：
  名称：

  Bromine catalyzed conversion of S-tert-butyl groups into versatile and, for self-assembly processes accessible, acetyl-protected thiols

  摘要：

  在乙酰氯和乙酸存在的情况下，通过催化溴的用量，将叔丁基保护基团简便高效地转化为硫醇的乙酰基保护基团。这种相当温和的反应条件对于硫官能化目标结构的新保护基策略具有特别重要的意义。

  DOI：

  10.1039/b408677e

文献信息

• Two-Terminal Molecular Memory through Reversible Switching of Quantum Interference Features in Tunneling Junctions
  作者：Marco Carlotti、Saurabh Soni、Sumit Kumar、Yong Ai、Eric Sauter、Michael Zharnikov、Ryan C. Chiechi

  DOI：10.1002/anie.201807879

  日期：2018.11.26

  Large‐area molecular tunneling junctions comprising self‐assembled monolayers of redox‐active molecules are described that exhibit two‐terminal bias switching. The as‐prepared monolayers undergo partial charge transfer to the underlying metal substrate (Au, Pt, or Ag), which converts their cores from a quinoid to a hydroquinoid form. The resulting rearomatization converts the bond topology from a cross‐conjugated

  描述了由氧化还原活性分子自组装单层组成的大面积分子隧道结，其表现出两端偏压切换。所制备的单层经历部分电荷转移到下面的金属基底（Au、Pt或Ag），这将它们的核心从醌型转化为氢醌形式。由此产生的重芳构化将键拓扑从交叉共轭转化为线性共轭 π 系统。交叉共轭形式与透射谱中干涉特征的出现相关，该干涉特征对于线性共轭形式消失。由于吸电子腈基的存在，还原电位和干涉特征接近金属基底的功函数和费米能级。我们利用共轭模式和量子干涉之间的关系，使用共晶 Ga-In 作为顶部接触，在原型器件中创建非易失性存储器。
• Correlations between Molecular Structure and Single-Junction Conductance: A Case Study with Oligo(phenylene-ethynylene)-Type Wires
  作者：Veerabhadrarao Kaliginedi、Pavel Moreno-García、Hennie Valkenier、Wenjing Hong、Víctor M. García-Suárez、Petra Buiter、Jelmer L. H. Otten、Jan C. Hummelen、Colin J. Lambert、Thomas Wandlowski

  DOI：10.1021/ja211555x

  日期：2012.3.21

  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.
• Formation of High-Quality Self-Assembled Monolayers of Conjugated Dithiols on Gold: Base Matters
  作者：Hennie Valkenier、Everardus H. Huisman、Paul A. van Hal、Dago M. de Leeuw、Ryan C. Chiechi、Jan C. Hummelen

  DOI：10.1021/ja110358t

  日期：2011.4.6

  This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases and studied the quality of the resulting SAMs on gold. We found that the optimal conditions to reproducibly form dense, high-quality monolayers are 9-15% triethylamine (Et3N) in THF. The deprotection base tetrabutylammonium hydroxide (Bu4NOH) leads to less dense SAMs and the incorporation of Bu4N into the monolayer. Furthermore, our results show the importance of the equilibrium concentrations of (di)thiolate in solution on the quality of the SAM. To demonstrate the relevance of these results for molecular electronics applications, large-area molecular junctions were fabricated using no base, Et3N, and Bu4NOH. The magnitude of the current-densities in these devices is highly dependent on the base. A value of beta = 0.15 angstrom(-1) for the exponential decay of the current-density of OPEs of varying length formed using Et3N was obtained.
• Bismuth(III)-Promoted Acetylation of Thio­ethers into Thioacetates
  作者：Martyn Jevric、Anne Ugleholdt Petersen、Mads Mansø、Anders Østergaard Madsen、Mogens Brøndsted Nielsen

  DOI：10.1002/ejoc.201500420

  日期：2015.7

  including molecules incorporating dithiafulvene, dicyanoethylene, dihydroazulene, fulleropyrrolidine, and triazole units, and successfully subjected to a BiIII promoted conversion into products with thioacetate end-cap(s). The azide group could also withstand these conditions, which allowed us to prepare S-(4-azidophenyl) ethanethioate that presents a convenient building block for subsequent CuAAC reactions

  硫代乙酸酯基团被广泛用作锚定基团，用于将分子连接到金表面或分子电子学中的电极之间。由于其易于水解，因此通常将其掺入相应的叔丁基硫醚合成序列的最后一步。在这里，我们提出了一种特别方便的方法，将 AcCl 与 Bi(OTf)3 结合使用，Bi(OTf)3 被称为对环境友好的盐。制备了多种具有叔丁基硫醚封端的氧化还原活性和光活性底物，包括结合二硫富烯、二氰基乙烯、二氢薁、富勒吡咯烷和三唑单元的分子，并成功地进行了 BiIII 促进转化为具有硫代乙酸酯封端。叠氮化物组也可以承受这些条件，
• Bromine catalyzed conversion of S-tert-butyl groups into versatile and, for self-assembly processes accessible, acetyl-protected thiols
  作者：Alfred Błaszczyk、Mark Elbing、Marcel Mayor

  DOI：10.1039/b408677e

  日期：——

  The facile and efficient conversion of a tert-butyl protecting group to an acetyl protecting group for thiols by catalytic amounts of bromine in acetyl chloride and the presence of acetic acid has been developed. The fairly mild reaction conditions are of particular interest for new protecting group strategies for sulfur functionalised target structures.

  在乙酰氯和乙酸存在的情况下，通过催化溴的用量，将叔丁基保护基团简便高效地转化为硫醇的乙酰基保护基团。这种相当温和的反应条件对于硫官能化目标结构的新保护基策略具有特别重要的意义。