(E)-3-Ethynyl-1,6-bis-triisopropylsilanyl-4-trimethylsilanylethynyl-hex-3-ene-1,5-diyne | 177500-66-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (E)-3-Ethynyl-1,6-bis-triisopropylsilanyl-4-trimethylsilanylethynyl-hex-3-ene-1,5-diyne
• 英文别名: [(E)-3-ethynyl-4-(2-trimethylsilylethynyl)-6-tri(propan-2-yl)silylhex-3-en-1,5-diynyl]-tri(propan-2-yl)silane
• CAS: 177500-66-2
• 化学式: C₃₁H₅₂Si₃
• 分子量: 509.01
• InChiKey: WHDIPKYNUWYSPK-NVQSTNCTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.24
• 重原子数：
  34
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (E)-3-Ethynyl-1,6-bis-triisopropylsilanyl-4-trimethylsilanylethynyl-hex-3-ene-1,5-diyne 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 四丁基溴化铵 、 potassium carbonate 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 16.5h， 生成 {(E)-4-Ethynyl-6-triisopropylsilanyl-3-[(triisopropylsilanyl)-ethynyl]-hex-3-ene-1,5-diynyl}-benzene
  参考文献：
  名称：

  Photoswitchable Tetraethynylethene-Dihydroazulene Chromophores

  摘要：

  The synthesis. characterization, and photophysical as well as electrochemical properties of the photochromic hybrid systems 11-16 and 18, which contain photoswitchable tetraethynylethene (TEE: 3,4-diethynylhex-3-ene-1,5-diyne) and dihydroazulene (DHA) moieties, are presented. The molecular photoswitches were synthesized by a Sonogashira cross-coupling reaction between an appropriate TEE precursor (6-10 and 17) and an iodinated DHA 1 or its vinylheptafulvene (VHF) isomer (4) (Schemes 5-7). X-Ray crystal structures of five DHA derivatives (1. trans-11a, cis-11a, 12, and 13) are discussed (Figs. 2-5). In all compounds, the cyclohexatriene moiety of the DHA chromophore adopts a clear boat conformation (Table I). presumably due to crystal-packing effects. the arylated TEE moieties in the hybrid systems show substantial distortions from planarity, with the dihedral angles between the plants of the central TEE core and thr adjacent aryl substituents amounting to 43. The switching properties were investigated by electronic absorption spectroscopy. Upon light absorption. DHAs 1. 12-16. and 18 underwent retro-electrocyclization in solution to give the corresponding VHFs( Figs h. II. and 12). The reaction is thermally reversible, with half-lives tau (1,2) between 3.9 and 5.8 h at 2.5 in CH2Cl2 (Figs. 7 and 13 and Table 3). A comparatively slower (E) - (Z) isomerization process about the central C=C bond of the TEE moiety was also observed. The N,N-dimethylanilino-(DMA) substituted TEE-DHA hybrid systems trans-11a and cis-11a did not react to the corresponding VHFs upon irradiation (Scheme 9). Instead. only the reversible (E) - (Z) photoisomerization of the TEE core occurred (Fig. 10 and Table S). This process was further investigated for photofatigue bq electronic-emission spectroscopy (Fig. 17). After protonation of the DMA group, the usual DHA - VHF photoreaction took place. Compound 11 represents a three-way chromophoric molecular switch with three addressable sub-units (TEE core, DHA/VHF moiety, and proton sensitive DMA group) that can undergo individual. reversible switching cycles (Scheme 9). A process modeling the function of an 'AND' logic gate (Fig. 19) and three writc/erase processes could be performed with this system. Cyclic and linear sweep-voltammetry studies in CH2Cl2 (+ Bu4NPF6) revealed the occurrence of characteristic first-reduction steps in the TEE-DHA hybrid systems between - 1.6 and - 1.8 V L'S. Fc/Fc. (ferrocene/ferricinium couple) (Table 5). Oxidations occur at cn. +1.10 V. After photoisomerization to the VHF derivatives. reduction steps at more positive and oxidation steps at mt,re negative potentials H ere recorded. No DHA - VHF isomerization took place upon electrochemical oxidation or reduction (Fig. 20).

  DOI：

  10.1002/1522-2675(20010418)84:4<743::aid-hlca743>3.0.co;2-1
• 作为产物：
  描述：

  (E)-1,1,6,6-tetrabromo-3,4-bis<(triisopropylsilyl)ethynyl>hexa-1,3,5-triene 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.5h， 生成 (E)-3-Ethynyl-1,6-bis-triisopropylsilanyl-4-trimethylsilanylethynyl-hex-3-ene-1,5-diyne
  参考文献：
  名称：

  供体/受体取代的四乙炔：用于先进材料的分子的系统组装

  摘要：

  制备了带有电子给体（对甲氧基苯基或对氨基苯基）和/或电子接受性（对硝基苯基）基团的一系列全面的四乙炔基（= 3,4-二乙炔基己烯-3-烯-1,5-二炔，TEE）通过[Pd]催化的Sonogashira交叉偶联反应。研究了这些分子的电子和光子特性，并特别强调了由中心TEE核心周围的供体/受体取代程度和模式所引起的影响。该分析表明，分子内供体-受体相互作用（如长波长电荷转移带所证明）在TEE 44和46中显着更有效，反式和顺，线性缀合供体和受体之间的电子通路，比11，与孪位的，交叉共轭的电子通道。UV / VIS光谱揭示的最长波长吸收带（λ的稳定红移最大）作为供体-受体共轭路径的数目在从双-芳基化的变化增加（11，44，和46），以四-芳基化（14 ，31和35）TEE。还发现最长波长吸收的位置强烈依赖于R 2 NC 6 H 4中N-取代基的性质。-捐助团体。电子发射光谱研究表明，供体-受体取

  DOI：

  10.1002/hlca.19960790818

文献信息

• Donor/Acceptor-Substituted Tetraethynylethenes: Systematic Assembly of Molecules for Use as Advanced Materials
  作者：Rik R. Tykwinski、Martin Schreiber、Raquel Pérez Carlón、François Diederich、Volker Gramlich

  DOI：10.1002/hlca.19960790818

  日期：1996.12.11

  such as 11 or 44, in agreement with the presence of highly polarized excited states in these molecules. Correspondingly, fluorescence spectra of TEEs bearing only donor or acceptor substituents showed little solvent dependency. The large majority of the donor/acceptor-substituted TEEs are thermally and environmentally stable molecules. They can be stored for months as solids in the air at room temperature

  制备了带有电子给体（对甲氧基苯基或对氨基苯基）和/或电子接受性（对硝基苯基）基团的一系列全面的四乙炔基（= 3,4-二乙炔基己烯-3-烯-1,5-二炔，TEE）通过[Pd]催化的Sonogashira交叉偶联反应。研究了这些分子的电子和光子特性，并特别强调了由中心TEE核心周围的供体/受体取代程度和模式所引起的影响。该分析表明，分子内供体-受体相互作用（如长波长电荷转移带所证明）在TEE 44和46中显着更有效，反式和顺，线性缀合供体和受体之间的电子通路，比11，与孪位的，交叉共轭的电子通道。UV / VIS光谱揭示的最长波长吸收带（λ的稳定红移最大）作为供体-受体共轭路径的数目在从双-芳基化的变化增加（11，44，和46），以四-芳基化（14 ，31和35）TEE。还发现最长波长吸收的位置强烈依赖于R 2 NC 6 H 4中N-取代基的性质。-捐助团体。电子发射光谱研究表明，供体-受体取
• Photoswitchable Tetraethynylethene-Dihydroazulene Chromophores
  作者：Luca Gobbi、Paul Seiler、François Diederich、Volker Gramlich、Corinne Boudon、Jean-Paul Gisselbrecht、Maurice Gross

  DOI：10.1002/1522-2675(20010418)84:4<743::aid-hlca743>3.0.co;2-1

  日期：2001.4.18

  The synthesis. characterization, and photophysical as well as electrochemical properties of the photochromic hybrid systems 11-16 and 18, which contain photoswitchable tetraethynylethene (TEE: 3,4-diethynylhex-3-ene-1,5-diyne) and dihydroazulene (DHA) moieties, are presented. The molecular photoswitches were synthesized by a Sonogashira cross-coupling reaction between an appropriate TEE precursor (6-10 and 17) and an iodinated DHA 1 or its vinylheptafulvene (VHF) isomer (4) (Schemes 5-7). X-Ray crystal structures of five DHA derivatives (1. trans-11a, cis-11a, 12, and 13) are discussed (Figs. 2-5). In all compounds, the cyclohexatriene moiety of the DHA chromophore adopts a clear boat conformation (Table I). presumably due to crystal-packing effects. the arylated TEE moieties in the hybrid systems show substantial distortions from planarity, with the dihedral angles between the plants of the central TEE core and thr adjacent aryl substituents amounting to 43. The switching properties were investigated by electronic absorption spectroscopy. Upon light absorption. DHAs 1. 12-16. and 18 underwent retro-electrocyclization in solution to give the corresponding VHFs( Figs h. II. and 12). The reaction is thermally reversible, with half-lives tau (1,2) between 3.9 and 5.8 h at 2.5 in CH2Cl2 (Figs. 7 and 13 and Table 3). A comparatively slower (E) - (Z) isomerization process about the central C=C bond of the TEE moiety was also observed. The N,N-dimethylanilino-(DMA) substituted TEE-DHA hybrid systems trans-11a and cis-11a did not react to the corresponding VHFs upon irradiation (Scheme 9). Instead. only the reversible (E) - (Z) photoisomerization of the TEE core occurred (Fig. 10 and Table S). This process was further investigated for photofatigue bq electronic-emission spectroscopy (Fig. 17). After protonation of the DMA group, the usual DHA - VHF photoreaction took place. Compound 11 represents a three-way chromophoric molecular switch with three addressable sub-units (TEE core, DHA/VHF moiety, and proton sensitive DMA group) that can undergo individual. reversible switching cycles (Scheme 9). A process modeling the function of an 'AND' logic gate (Fig. 19) and three writc/erase processes could be performed with this system. Cyclic and linear sweep-voltammetry studies in CH2Cl2 (+ Bu4NPF6) revealed the occurrence of characteristic first-reduction steps in the TEE-DHA hybrid systems between - 1.6 and - 1.8 V L'S. Fc/Fc. (ferrocene/ferricinium couple) (Table 5). Oxidations occur at cn. +1.10 V. After photoisomerization to the VHF derivatives. reduction steps at more positive and oxidation steps at mt,re negative potentials H ere recorded. No DHA - VHF isomerization took place upon electrochemical oxidation or reduction (Fig. 20).