4,4'-(3-(1-(triisopropylsilyl)penta-1,4-diyn-3-ylidene)penta-1,4-diyne-1,5-diyl)bis(N,N-dimethylaniline) | 860806-36-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4,4'-(3-(1-(triisopropylsilyl)penta-1,4-diyn-3-ylidene)penta-1,4-diyne-1,5-diyl)bis(N,N-dimethylaniline)
• CAS: 860806-36-6
• 化学式: C₃₅H₄₂N₂Si
• 分子量: 518.817
• InChiKey: VYSRTLZPVHKCJS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.37
• 重原子数：
  38.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  4,4'-(3-(1-(triisopropylsilyl)penta-1,4-diyn-3-ylidene)penta-1,4-diyne-1,5-diyl)bis(N,N-dimethylaniline) 在 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 二氯甲烷 为溶剂， 以46 mg的产率得到1,12-Bis[4-(N,N-dimethylamino)phenyl]-3,10-bis{[4-(N,N-dimethylamino)phenyl]ethynyl}-4,9-bis[(triisopropylsilyl)ethynyl]-dodeca-3,9-diene-1,5,7,11-tetrayne
  参考文献：
  名称：

  Highly Functionalized Dimeric Tetraethynylethenes and Expanded Radialenes: Strong Evidence for Macrocyclic Cross-Conjugation

  摘要：

  A selection of dimeric tetra-ethynylethenes (TEEs) and perethynylated expanded radialenes, containing different donor/acceptor substitution patterns, have been prepared and fully characterized. The first X-ray crystal structure of an expanded [6]radialene, with twelve peripheral 3,5-di(tert-butyl)phenyl substituents, is presented. This macrocycle, the all-carbon core of which is isomeric with fullerene C-60, adopts a non-planar, "chair-like" conformation. Also a TEE dimer, carrying NN-dimethylaniline donor substituents, has been subjected to an X-ray crystallo graphic analysis. The electronic properties were studied by UV/Vis spectroscopy and electrochemistry, providing fundamental insight into mechanisms of pi -electron delocalization in the acyclic and macrocyclic chromophores. Donor or donor-acceptor-substituted dimeric TEE derivatives show very strong absorptions extending over the entire UV/Vis region; their longest wavelength absorption bands have high charge-transfer character. Macrocyclic cross-conjugation in the expanded radialenes becomes increasingly efficient with increasing donor-acceptor polarization. A dual, strongly solvent-polarity-dependent fluorescence was observed for a tetrakis(NN-dimethylaniline)-substituted dimeric TEE; this interesting emission behavior is explained by the twisted intramolecular charge-transfer (TICT) state model. Donor-substituted expanded radialenes display huge resonance-enhanced third-order nonlinear optical coefficients.

  DOI：

  10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3
• 作为产物：
  描述：

  [3-(二溴亚甲基)-5-(三甲基甲硅烷基)-1,4-戊二炔-1-基]三(1-甲基乙基)硅烷 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 42.0h， 生成 4,4'-(3-(1-(triisopropylsilyl)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-Substituted Cyanoethynylethenes: π-Conjugation and Band-Gap Tuning in Strong Charge-Transfer Chromophores
  作者：Nicolle N. P. Moonen、William C. Pomerantz、Robin Gist、Corinne Boudon、Jean-Paul Gisselbrecht、Tsuyoshi Kawai、Atsushi Kishioka、Maurice Gross、Masahiro Irie、François Diederich

  DOI：10.1002/chem.200500082

  日期：2005.5.20

  combination of 13C NMR spectroscopic and electrochemistry measurements. Donor-substituted CEEs display strong intramolecular charge-transfer (CT) character, resulting in intense, bathochromically shifted CT bands in the UV/Vis spectrum. Their structural diversity establishes them as suitable models for the study of pi-conjugation and band gap tuning in strong charge-transfer chromophores. The extent of pi-conjugation

  合成了一系列广泛的甲硅烷基保护的氰基乙炔（CEE）和N，N-二甲基苯胺基供体取代的CEE。通过选择性的甲硅烷基脱保护和随后的氧化炔键偶联，可以构建更多的发色团。通过13 C NMR光谱学和电化学测量的结合揭示了CEE的强电子接受性质。供体取代的CEE表现出很强的分子内电荷转移（CT）特性，导致在UV / Vis光谱中出现强烈的红移的CT带。它们的结构多样性使它们成为研究强电荷转移生色团的π共轭和能带隙调谐的合适模型。通过结合基态技术研究了供体取代的CEE中pi共轭的程度，例如X射线晶体学，电化学，B3 LYP计算和NMR光谱学。将这些基态结果与在UV / Vis光谱中观察到的特征进行比较后发现，与预期相反，更广泛的pi共轭可导致具有强供体和受体部分的分子带隙更大。
• 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.