Dimethyl-(4-{(E)-6-triisopropylsilanyl-3-[(triisopropylsilanyl)-ethynyl]-4-trimethylsilanylethynyl-hex-3-ene-1,5-diynyl}-phenyl)-amine | 177500-70-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Dimethyl-(4-{(E)-6-triisopropylsilanyl-3-[(triisopropylsilanyl)-ethynyl]-4-trimethylsilanylethynyl-hex-3-ene-1,5-diynyl}-phenyl)-amine
• 英文别名: N,N-dimethyl-4-[(E)-4-(2-trimethylsilylethynyl)-6-tri(propan-2-yl)silyl-3-[2-tri(propan-2-yl)silylethynyl]hex-3-en-1,5-diynyl]aniline
• CAS: 177500-70-8
• 化学式: C₃₉H₆₁NSi₃
• 分子量: 628.177
• InChiKey: OQOZFBIVCBVQNZ-HEFFKOSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.72
• 重原子数：
  43
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Dimethyl-(4-{(E)-6-triisopropylsilanyl-3-[(triisopropylsilanyl)-ethynyl]-4-trimethylsilanylethynyl-hex-3-ene-1,5-diynyl}-phenyl)-amine 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 水 、 三乙胺 为溶剂， 反应 14.0h， 生成 (E)-1-[4-(dimethylamino)phenyl]-6-(5-nitro-2-thienyl)-3,4-bis-[2-(triisopropylsilyl)ethynyl]hex-3-ene-1,5-diyne
  参考文献：
  名称：

  Donor-Acceptor-Functionalized Tetraethynylethenes with Nitrothienyl Substituents: Structure-Property Relationships

  摘要：

  Tetraethynylethenes (TEEs) functionalized with donor (4-(dimethylamino)phenyl) and acceptor (5-nitro-2-thienyl) groups were prepared by Pd-0-catalyzed Sonogashira cross-coupling reactions (Schemes 1-6). The physical properties of these novel chromophores were examined and compared with those of analogous systems containing 4-nitrophenyl instead of 5-nitro-2-thienyl acceptor groups. X-Ray crystal-structure analyses showed the pi-conjugated frameworks of 2, 11, and 13, including the TEE core and all aryl moieties, to be nearly perfectly planar (Figs. 1, 3, and 4). Ln contrast, one 4-(dimethylamino)phenyl group in 10 is rotated almost 90 degrees out of the molecular plane, presumably due to crystal-packing effects (Fig. 2). The analysis of bond lengths and bond angles revealed little, if any, evidence of intramolecular ground-state donor-acceptor interactions. The electrochemical behavior of nitrothienyl-substituted TEEs is similar to that of the corresponding nitrophenyl-functionalized derivatives (Table 3). The nitrothienyl groups were reduced at -1.23 V (vs. the ferrocene/ferricinium couple, Fc/Fc(+)), regardless of the degree or pattern of other substitutions. For nonsymmetrical TEE 13, the reduction of the nitrothienyl group at - 1.23 V is followed by a reduction of the nitrophenyl group at - 1.40 V, a potential typical for the reduction of other nitrophenyl-substituted TEEs, such as 17-20. UV/VIS Spectroscopy showed a consistently lower-energy absorption cutoff for nitrothienyl derivatives compared with the analogous nitrophenyl-substituted TEEs that confirms a lowering of the HOMO-LUMO gap as a result of nitrothiophene substitution (Figs. 5 and 6). A comparison of the tetrakis-arylated TEEs 11, 13, and 20 clearly showed a steady bathochromic shift of the longest-wavelength absorption maximum and the end-absorption upon sequential replacement of nitrophenyl by nitrothienyl groups. Quantum-chemical computations were performed to explain a number of complex features of the electronic absorption spectra. All empirical features of relevance in the experimental UV/VIS spectra for 2, 5, 6, and 17-19 were correctly reproduced by computation (Tables 4 and 5). The combination of theory and experiment was found to be very useful to explain the particular acceptor properties of the 5-nitro-2-thienyl group.

  DOI：

  10.1002/1522-2675(20000705)83:7<1484::aid-hlca1484>3.0.co;2-1
• 作为产物：
  描述：

  (E)-1,1-Dibromo-6-triisopropylsilanyl-3-[(triisopropylsilanyl)-ethynyl]-4-trimethylsilanylethynyl-hexa-1,3-dien-5-yne 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 正丁基锂 、 三乙胺 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 25.0h， 生成 Dimethyl-(4-{(E)-6-triisopropylsilanyl-3-[(triisopropylsilanyl)-ethynyl]-4-trimethylsilanylethynyl-hex-3-ene-1,5-diynyl}-phenyl)-amine
  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

• 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).