4,4'-((1E,1'E)-(2,5-diiodo-1,4-phenylene)bis(ethene-2,1-diyl))bis(N,N-dibutylaniline) | 660870-78-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 4,4'-((1E,1'E)-(2,5-diiodo-1,4-phenylene)bis(ethene-2,1-diyl))bis(N,N-dibutylaniline)
• CAS: 660870-78-0
• 化学式: C₃₈H₅₀I₂N₂
• 分子量: 788.637
• InChiKey: RHIHYJTWUSKHHZ-IWGRKNQJSA-N

物化性质

• 沸点：
  758.3±60.0 °C(Predicted)
• 密度：
  1.373±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.05
• 重原子数：
  42.0
• 可旋转键数：
  18.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 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'-((1E,1'E)-(2,5-diiodo-1,4-phenylene)bis(ethene-2,1-diyl))bis(N,N-dibutylaniline) 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三氟乙酸 作用下， 以 四氢呋喃 、 哌啶 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 4,4'-[{2,5-bis[(E)-4-(dibutylamino)styryl]-1,4-phenylene}bis(ethyne-2,1-diyl)]diphenol
  参考文献：
  名称：

  羟基二烷基氨基十字形：具有独特光物理性质的两性材料

  摘要：

  两个两性十字形6和7（XF; 4,4'-[（（1 E，1'E））-（2,5-双{[4-（二丁基氨基）苯基]乙炔基} -1,4-亚苯基）bis（乙烯-2,1-二基]]二酚，4,4'-[{2,5-双[[ E）-4-（二丁基氨基）苯乙烯基] -1,4-亚苯基}双（乙炔-2,1-通过霍纳反应，随后的Sonogashira偶联和随后的脱保护反应来制备二甲酰基]二酚）。XFs暴露于三氟乙酸，氢氧化四丁铵和金属三氟甲磺酸酯时，在吸收和发射方面显示出显着变化。6和7的替换模式导致前沿分子轨道的空间分离，这使得XF的HOMO或LUMO可以由酸性或碱性试剂独立处理。XF 6在苯乙烯轴上具有羟基，在八种不同溶剂中接触十种胺后，其发射颜色会发生变化。通过线性判别分析来分析添加胺后的荧光变化。这些XF在金属阳离子和胺的传感器应用中可能具有潜力。

  DOI：

  10.1002/chem.201002865
• 作为产物：
  描述：

  1,4-双(溴甲基)-2,5-二碘苯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 4,4'-((1E,1'E)-(2,5-diiodo-1,4-phenylene)bis(ethene-2,1-diyl))bis(N,N-dibutylaniline)
  参考文献：
  名称：

  Cruciforms as Functional Fluorophores:  Response to Protons and Selected Metal Ions

  摘要：

  The photophysics of dialkylamino- and/or pyridine-containing functional chromophores, 1,4-distyryl-2,5-bis(ethynylaryl) benzenes (cruciforms) was investigated; their fluorescence quantum yields and emissive lifetimes were determined. Depending upon their substituents, the frontier molecular orbitals (FMOs) of these cruciforms are either congruent, i.e., HOMO and LUMO occupy the same real space, or disjoint, i.e., the HOMO is located on one branch of the cruciform while the LUMO is located on the second one. Donor-acceptor substitution leads to a disjoint FMO pattern, while the parent 1,4-distyryl-2,5-bis(phenylethynyl)benzene shows congruent FMOs. The photophysics of the cruciforms was investigated upon addition of either an excess of trifluoroacetic acid or an excess of selected metal (Mg2+, Ca2+, Mn2+, Zn2+) trifluoromethanesulfonate salts. Addition of either metal ions or protons led to analogous but not identical changes in the spectroscopic properties of the investigated cruciforms. The collected data suggest that the metals bind preferentially at the aniline nitrogen and not at the electron-rich arene. The spatially separated FMOs permit the independent manipulation of the HOMO and the LUMO of such cruciforms. If the branches contain metal-complexing moieties, metal binding leads to either a hypsochromic or a bathochromic shift in emission via interaction of the metal cations with either the HOMO or the LUMO.

  DOI：

  10.1021/ja061112e

文献信息

• Cruciform π-systems: hybrid phenylene-ethynylene/phenylene-vinylene oligomers
  作者：James N. Wilson、Mira Josowicz、Yiqing Wang、Uwe H. F. Bunz

  DOI：10.1039/b312156a

  日期：——

  The cruciform pentamers 3a–g were synthesized by a combined Horner–Sonogashira approach; their band gaps vary significantly with emission varying from blue to red depending upon their substituent pattern.

  十字形五聚物3a-g是通过联合Horner-Sonogashira方法合成的；它们的带隙差异显著，发射颜色根据取代基的不同模式从蓝色变化到红色。
• The Photophysics of Pyridine-Derivatized<i>ortho</i>-,<i>meta</i>-, and<i>para</i>-Dibutylamino Cruciforms
  作者：Florian Hinderer、Uwe H. F. Bunz

  DOI：10.1002/chem.201300211

  日期：2013.6.24

  AbstractThe photophysical properties of a series of para‐substituted donor–acceptor cruciform fluorophores (p1–4) were investigated and compared with their meta and ortho isomers (m1–4 and o1–4). The structural variations were found to have a significant effect on the solvatochromism, fluorescence quantum yields (Φfl), fluorescence lifetimes (τfl), and response upon addition of trifluoroacetic acid. The observed spectral shifts in absorption and emission caused by protonation of the cruciforms make them promising candidates as chemosensors. Additional computational studies provided more insight into the electronic structure of the systems.
• Switching of Intramolecular Charge Transfer in Cruciforms:  Metal Ion Sensing
  作者：James N. Wilson、Uwe H. F. Bunz

  DOI：10.1021/ja050017n

  日期：2005.3.1

  Three different cruciforms containing the 1,4-bis-4'-pyridylethynyl-2,5-distyrylbenzene or the 1,4-bis-phenylethynyl-2,5-distyrylbenzene unit were synthesized and investigated with respect to their metal sensing properties. Upon addition of metal cations to these cruciforms, either a bathochromic or hypsochromic shift in emission and absorption is observed. The shift depends on whether the metal coordinates preferentially to the pyridine or to the dibutylaniline branches of the cruciforms. The three cruciforms were exposed to a selection of metal cations in dichloromethane, and their emission was examined. The cruciforms show differential sensing of metal cations, that is, different metals can be specifically discerned upon exposure to three cruciforms but not when exposed to only one. The system can discern calcium from magnesium cations and silver from mercury or lithium cations.
• Synthesis and electronic properties of bis-styryl substituted trimeric aryleneethynylenes. Comparison of cruciforms with iso-cruciforms
  作者：James N. Wilson、Kenneth I. Hardcastle、Mira Josowicz、Uwe H.F. Bunz

  DOI：10.1016/j.tet.2004.06.040

  日期：2004.8

  Four 1,2-distyryl-4,5-bis(phenylethynyl)benzenes are described. A two step synthesis, a combination of Homer and Sonogashira methods is utilized. The targets and their para isomers were examined by UV-vis and fluorescence spectroscopies as well as by cyclic voltammetry. They show solvatochromic behavior and are easily oxidized if the styryl units carry dialkylamino substitutents. Single crystal structures of three derivatives have been obtained. (C) 2004 Elsevier Ltd. All rights reserved.