4,4'-(3-(penta-1,4-diyn-3-ylidene)penta-1,4-diyne-1,5-diyl)bis(N,N-dimethylaniline) | 860806-37-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4,4'-(3-(penta-1,4-diyn-3-ylidene)penta-1,4-diyne-1,5-diyl)bis(N,N-dimethylaniline)
• CAS: 860806-37-7
• 化学式: C₂₆H₂₂N₂
• 分子量: 362.474
• InChiKey: AFYKWCYMEFOUNA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.78
• 重原子数：
  28.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  6.48
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4-硝基碘苯 、 4,4'-(3-(penta-1,4-diyn-3-ylidene)penta-1,4-diyne-1,5-diyl)bis(N,N-dimethylaniline) 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 18.0h， 以63%的产率得到1-[4-(dimethylamino)phenyl]-3-{[4-(dimethylamino)phenyl]ethynyl}-6-(4-nitrophenyl)-4-[(4-nitrophenyl)ethynyl]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
• 作为产物：
  描述：

  1-[4-(dimethylamino)phenyl]-3-{[4-(dimethylamino)phenyl]ethynyl}-6-(triisopropylsilyl)-4-[(triisopropylsilyl)ethynyl]hex-3-ene-1,5-diyne 在 四丁基氟化铵 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 0.5h， 生成 4,4'-(3-(penta-1,4-diyn-3-ylidene)penta-1,4-diyne-1,5-diyl)bis(N,N-dimethylaniline)
  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-Functionalized Tetraethynylethenes with Nitrothienyl Substituents: Structure-Property Relationships
  作者：Rik R. Tykwinski、Anouk Hilger、François Diederich、Hans Peter Lüthi、Paul Seiler、Volker Gramlich、Jean-Paul Gisselbrecht、Corinne Boudon、Maurice Gross

  DOI：10.1002/1522-2675(20000705)83:7<1484::aid-hlca1484>3.0.co;2-1

  日期：2000.7.5

  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.