((2,5-bis(phenylethynyl)-1,4-phenylene)bis(methoxymethanetriyl))tetrabenzene | 1189114-51-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: ((2,5-bis(phenylethynyl)-1,4-phenylene)bis(methoxymethanetriyl))tetrabenzene
• 英文别名: 1,4-Bis[methoxy(diphenyl)methyl]-2,5-bis(2-phenylethynyl)benzene
• CAS: 1189114-51-9
• 化学式: C₅₀H₃₈O₂
• 分子量: 670.851
• InChiKey: KGICRERZGQBZKA-UHFFFAOYSA-N

物化性质

• 熔点：
  253-255 °C
• 沸点：
  761.9±60.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.6
• 重原子数：
  52
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ((2,5-bis(phenylethynyl)-1,4-phenylene)bis(methoxymethanetriyl))tetrabenzene 在 萘 、 lithium 、 1,2-二碘乙烷 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以83%的产率得到3,7-diiodo-1,1,2,5,5,6-hexaphenyl-1,5-dihydro-s-indacene
  参考文献：
  名称：

  Modular Synthesis of 1H-Indenes, Dihydro-s-Indacene, and Diindenoindacene—a Carbon-Bridged p-Phenylenevinylene Congener

  摘要：

  A variety of 1H-indenes, dihydro-s-indacenes, and diindenoindacenes, carbon-bridged phenylenevinylene derivatives, can be synthesized,in good to high yields using as a synthetic module a 3-lithioindene compound made available by reductive cyclization of an alkynylbenzene derivative. The planar analogues of oligophenylenevinylene compounds thus synthesized show physical properties beneficial for use as ambipolar organic semiconductor materials.

  DOI：

  10.1021/ja905626b
• 作为产物：
  描述：

  甲醇 、 1,4-bis(phenylethynyl)-2,5-bis(diphenylhydroxymethyl)benzene 在 ammonium cerium (IV) nitrate 作用下， 生成 ((2,5-bis(phenylethynyl)-1,4-phenylene)bis(methoxymethanetriyl))tetrabenzene
  参考文献：
  名称：

  铁催化的茚的 5-Endo-Dig 合成方法及其对窄带隙 π 系统的双向扩展

  摘要：

  茚骨架是多种化合物的关键结构，在医学和材料科学中具有应用。由于茚环的芳香性会暂时被破坏，传统的合成通常需要苛刻的条件或反应性中间体。为了解决这个问题，我们研究了铁催化的5-内环化反应来构建茚的五元碳环组分，该反应不会破坏苯环的芳香性。 FeCl 2与金属镁还原产生的还原铁反应物种是一种关键的反应物种，可以有效裂解起始材料中的 C-O 键，生成休眠自由基稳定的铁，该铁可以顺利地进行 5- 内切反应茚环的闭合。合成条件非常温和，我们合成了高最高占据分子轨道（HOMO）、窄带隙共轭化合物，其HOMO能级高达-4.59 eV，光学带隙为1.50 eV；因此，即使在空气中它也不稳定。

  DOI：

  10.1021/acscatal.3c04961

文献信息

• Large Electronic Coupling in a Homoconjugated Donor–Acceptor System Involving Carbon-bridged Oligo(<i>p</i>-phenylenevinylene) and Triazine
  作者：Junpei Sukegawa、Hayato Tsuji、Eiichi Nakamura

  DOI：10.1246/cl.140022

  日期：2014.5.5

  We have synthesized a new homoconjugated donor–acceptor (D–A) system featuring a rigid planar carbon-bridged oligo(p-phenylenevinylene) that shows efficient intramolecular charge separation (CS, 98%). The charge recombination rate is 100-times slower than that of CS, and located in the Marcus inverted region. The electronic coupling was estimated to be 1.0 × 103 cm−1, which is one of the largest values among reported D–A interactions.

  我们合成了一种新的同共轭供体-受体（D–A）系统，具有刚性平面碳桥接的寡(p-苯撑乙烯)，其显示出高效的分子内电荷分离（CS，98%）。电荷复合速率比电荷分离慢100倍，并位于Marcus反转区域。电子耦合被估计为1.0 × 10³ cm−1，这是已报告的D–A相互作用中最大的数值之一。
• Doubly Spiro-Conjugated Chiral Carbocycles Exhibiting SOMO–HOMO Inversion in Persistent Radical Cations
  作者：Takumi Sakamaki、Yan Zhang、Shota Fukuma、Carlos M. Cruz、Abel Cárdenas Valdivia、Araceli G. Campaña、Juan Casado、Rui Shang、Eiichi Nakamura

  DOI：10.1021/jacs.4c02404

  日期：2024.5.8

  Persistent chiral organic open-shell systems have captured growing interest due to their potential applications in organic spintronic and optoelectronic devices. Nevertheless, the integration of configurationally stable chirality into an organic open-shell system continues to pose challenges in molecular design. The π-extended skeleton incorporated in spiro-conjugated carbocycles can provide robust

  持久性手性有机开壳系统由于其在有机自旋电子和光电器件中的潜在应用而引起了越来越多的兴趣。然而，将构型稳定的手性整合到有机开壳系统中仍然对分子设计提出挑战。螺共轭碳环中的 π 延伸骨架可以提供强大的手性光学特性以及激发态和离子自由基态的显着稳定性。然而，在持久性有机开壳系统的设计中，这种方法的探索相对较少。我们在这里报道了双螺共轭碳环的( S,S )-、( R,R )-和内消旋异构体，其特征是通过两个螺环连接不同共轭长度的平坦和刚性碳桥对亚苯基乙烯撑( CPV )。碳中心，我们将其表示为D-spiro-CPV，因为它是准二聚体结构。我们基于双锂化环化方法的合成方法可以轻松生产D-spiro-CPV 。 D-spiro-CPV表现出具有高荧光量子产率 (Φ FL ) 的圆偏振发光 (CPL)，导致 CPL 亮度高达 21 M –1 cm –1 ，并且还表现出高热稳定性和光稳定性。 D-spir
• Carbon-Bridged Oligo(phenylenevinylene)s: Stable π-Systems with High Responsiveness to Doping and Excitation
  作者：Xiaozhang Zhu、Hayato Tsuji、Juan T. López Navarrete、Juan Casado、Eiichi Nakamura

  DOI：10.1021/ja309318s

  日期：2012.11.21

  The high responsiveness of pi-conjugated materials to external stimuli, such as electrons and photons, accounts for both their utility in optoelectronic applications and their chemical instability. Extensive studies on heteroatom-stabilized pi-conjugated systems notwithstanding, it is still difficult to combine high performance and stability. We report here that carbon-bridged oligo(p-phenylenevinylene)s (COPV-n) are not only more responsive to doping and photoexcitation but also more stable than the conventional p-phenylenevinylenes and poly(3-hexylthiophene), surviving photolysis very well in air, suggesting that they could serve as building blocks for optoelectronic applications. Activation of the ground state by installation of bond angle strain toward the doped or photoexcited state and the flat, rigid, and hindered structure endows COPVs with stimuli-responsiveness and stability without recourse to heteroatoms. For example, COPV-6 can be doped with an extremely small reorganization energy and form a bipolaron delocalized over the entire it system. Applications to bulk and molecular optoelectronic devices are foreseen.
• Air- and Heat-Stable Planar Tri-<i>p</i>-quinodimethane with Distinct Biradical Characteristics
  作者：Xiaozhang Zhu、Hayato Tsuji、Koji Nakabayashi、Shin-ichi Ohkoshi、Eiichi Nakamura

  DOI：10.1021/ja206060n

  日期：2011.10.19

  A heptacyclic carbocycle possessing three p-quinodimethane units conjugated in one plane has been synthesized and shown to exhibit distinct biradical characteristics. The molecule has a HOMO/LUMO band gap of ca. 1 eV and a S(0)-T(1) energy gap of 2.12 kcal/mol, and it absorbs and emits near-IR light at room temperature. It is air-stable under ambient light for several months and thermally stable up to 160 degrees C under nitrogen, and it undergoes reversible two-electron oxidation and reduction. The synthetic approach is such that a smaller and larger oligo-p-quinodimethane can be synthesized.