2-(4-{(E)-6-[4-(dimethylamino)phenyl]-3,4-bis[(triisopropylsilyl)ethynyl]hex-3-ene-1,5-diynyl}phenyl)-8aH-azulene-1,1-dicarbonitrile | 351459-78-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-(4-{(E)-6-[4-(dimethylamino)phenyl]-3,4-bis[(triisopropylsilyl)ethynyl]hex-3-ene-1,5-diynyl}phenyl)-8aH-azulene-1,1-dicarbonitrile
• 英文别名: 2-[4-[(E)-4-[2-[4-(dimethylamino)phenyl]ethynyl]-6-tri(propan-2-yl)silyl-3-[2-tri(propan-2-yl)silylethynyl]hex-3-en-1,5-diynyl]phenyl]-8aH-azulene-1,1-dicarbonitrile
• CAS: 351459-78-4
• 化学式: C₅₄H₆₃N₃Si₂
• 分子量: 810.285
• InChiKey: WTPXRAAHYNBZBK-QJGAVIKSSA-N

物化性质

• 沸点：
  822.9±65.0 °C(predicted)
• 密度：
  1.07±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.99
• 重原子数：
  59
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  50.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-{(E)-6-[4-(dimethylamino)phenyl]-3,4-bis[(triisopropylsilyl)ethynyl]hex-3-ene-1,5-diynyl}phenyl)-8aH-azulene-1,1-dicarbonitrile 以 二氯甲烷 为溶剂， 反应 3.5h， 以39%的产率得到2-(4-{(Z)-6-[4-(dimethylamino)phenyl]-3,4-bis[(triisopropylsilyl)ethynyl]hexx-3-ene-1,5-diinyl}phenyl)8aH-azulene-1,1-dicarbonitrile
  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-(4-iodophenyl)-1,8a-dihydroazulene-1,1-dicarbonitrile 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 四丁基溴化铵 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 10.5h， 生成 2-(4-{(E)-6-[4-(dimethylamino)phenyl]-3,4-bis[(triisopropylsilyl)ethynyl]hex-3-ene-1,5-diynyl}phenyl)-8aH-azulene-1,1-dicarbonitrile
  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

• A Novel Three-Way Chromophoric Molecular Switch: pH and Light Controllable Switching Cycles
  作者：Luca Gobbi、Paul Seiler、François Diederich

  DOI：10.1002/(sici)1521-3773(19990301)38:5<674::aid-anie674>3.0.co;2-0

  日期：1999.3.1

  Programmed with an unusual number of functions, the tetraethynylethene derivative 1 exhibits three addressable switching subunits, which can undergo individual reversible switching cycles that are controllable by pH and light. Three "write/erase" processes and one "AND" logic gate process can be separately addressed, and in each case an efficient nondestructive readout is possible.