(Z)-2-{3,4-bis[(triisopropylsilyl)ethynyl]-6-(trimethylsilyl)hex-3-ene-1,5-diynyl}thiophene | 351459-91-1

• 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: (Z)-2-{3,4-bis[(triisopropylsilyl)ethynyl]-6-(trimethylsilyl)hex-3-ene-1,5-diynyl}thiophene
• 英文别名: trimethyl-[(E)-4-(2-thiophen-2-ylethynyl)-6-tri(propan-2-yl)silyl-3-[2-tri(propan-2-yl)silylethynyl]hex-3-en-1,5-diynyl]silane
• CAS: 351459-91-1
• 化学式: C₃₅H₅₄SSi₃
• 分子量: 591.136
• InChiKey: ADBKEKRPIODXQC-JEIPZWNWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.72
• 重原子数：
  39
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-2-{3,4-bis[(triisopropylsilyl)ethynyl]-6-(trimethylsilyl)hex-3-ene-1,5-diynyl}thiophene 在 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 3.0h， 生成 2-{(E)-4-Ethynyl-6-triisopropylsilanyl-3-[(triisopropylsilanyl)-ethynyl]-hex-3-ene-1,5-diynyl}-thiophene
  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：

  2-碘噻吩 、 (E)-3-Ethynyl-1,6-bis-triisopropylsilanyl-4-trimethylsilanylethynyl-hex-3-ene-1,5-diyne 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以64%的产率得到(Z)-2-{3,4-bis[(triisopropylsilyl)ethynyl]-6-(trimethylsilyl)hex-3-ene-1,5-diynyl}thiophene
  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

文献信息

• 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).