4,4'-(1,4(1,4)-dibenzenacyclohexaphane-12,43-diylbis(ethene-2,1-diyl))bis(2,5-bis(hexyloxy)benzaldehyde) | 1269228-91-2

• 分子结构分类: 有机化合物
• 英文名称: 4,4'-(1,4(1,4)-dibenzenacyclohexaphane-12,43-diylbis(ethene-2,1-diyl))bis(2,5-bis(hexyloxy)benzaldehyde)
• CAS: 1269228-91-2
• 化学式: C₅₈H₇₆O₆
• 分子量: 869.238
• InChiKey: LKGMFLRKUOSNHY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.37
• 重原子数：
  64.0
• 可旋转键数：
  30.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  4,4'-(1,4(1,4)-dibenzenacyclohexaphane-12,43-diylbis(ethene-2,1-diyl))bis(2,5-bis(hexyloxy)benzaldehyde) 在 吡啶 、 四丁基溴化铵 、 palladium diacetate 、 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 4,4'-(((1,4(1,4)-dibenzenacyclohexaphane-12,43-diylbis(ethene-2,1-diyl))bis(2,5-bis(hexyloxy)-4,1-phenylene))bis(ethene-2,1-diyl))dibenzaldehyde
  参考文献：
  名称：

  Blending Through-Space and Through-Bond π–π-Coupling in [2,2′]-Paracyclophane-oligophenylenevinylene Molecular Wires

  摘要：

  A series of ZnP-pCp-oPPV-C-60 conjugates covalently connected through [2,2']-paracyclophane-oligophenylenevinylene (pCp-oPPV) bridges containing one, two, and three [2,2']-paracyclophanes (pCps) has been prepared in multistep synthetic procedures involving Horner-Wadsworth-Emmons olefination reactions and/or Heck type Pd-catalyzed reactions. Molecular modeling suggests that charge transfer is effectively mediated by the pCp-oPPVs through a predominant hole-transfer mechanism. Photophysical investigation supports molecular modeling and reveals two major trends. On one hand, C-60 excitation of 1, 2, and 3 leads exclusively to charge transfer between pCp and C-60 to afford a ZnP-(pCp-oPPV)(circle+)-C-60(circle-) radical ion pair state without giving rise to a subsequent charge shift to yield the ZnP circle+-pCp-oPPV-C-60(circle-) radical ion pair state. On the other hand, ZnP excitation of 1, 2, and 3 results in a rather slow charge transfer between ZnP and C-60, after which the ZnP circle+-pCp-oPPV-C-60(circle-) radical ion pair state evolves. In temperature-dependent ZnP fluorescence experiments, which were performed in the temperature range from 273 to 338 K, two domains are discernible: low and high temperature behaviors. In the low temperature range (i.e., below 30 degrees C) the rate constants do not change, suggesting that a superexchange mechanism is the modus operandi. In the high temperature range (i.e., >30 degrees C) the rate constants increase. Moreover, we find rather strong distance dependence for 1 and 2 and weak distance dependence for 2 and 3. A damping factor of 0.145 angstrom(-1) is derived for the former pair and 0.012 angstrom(-1) for the latter.

  DOI：

  10.1021/ja401239r
• 作为产物：
  描述：

  1,4-二(己氧基)-2,5-二碘苯 在 正丁基锂 、 四丁基溴化铵 、 palladium diacetate 、 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 生成 4,4'-(1,4(1,4)-dibenzenacyclohexaphane-12,43-diylbis(ethene-2,1-diyl))bis(2,5-bis(hexyloxy)benzaldehyde)
  参考文献：
  名称：

  Blending Through-Space and Through-Bond π–π-Coupling in [2,2′]-Paracyclophane-oligophenylenevinylene Molecular Wires

  摘要：

  A series of ZnP-pCp-oPPV-C-60 conjugates covalently connected through [2,2']-paracyclophane-oligophenylenevinylene (pCp-oPPV) bridges containing one, two, and three [2,2']-paracyclophanes (pCps) has been prepared in multistep synthetic procedures involving Horner-Wadsworth-Emmons olefination reactions and/or Heck type Pd-catalyzed reactions. Molecular modeling suggests that charge transfer is effectively mediated by the pCp-oPPVs through a predominant hole-transfer mechanism. Photophysical investigation supports molecular modeling and reveals two major trends. On one hand, C-60 excitation of 1, 2, and 3 leads exclusively to charge transfer between pCp and C-60 to afford a ZnP-(pCp-oPPV)(circle+)-C-60(circle-) radical ion pair state without giving rise to a subsequent charge shift to yield the ZnP circle+-pCp-oPPV-C-60(circle-) radical ion pair state. On the other hand, ZnP excitation of 1, 2, and 3 results in a rather slow charge transfer between ZnP and C-60, after which the ZnP circle+-pCp-oPPV-C-60(circle-) radical ion pair state evolves. In temperature-dependent ZnP fluorescence experiments, which were performed in the temperature range from 273 to 338 K, two domains are discernible: low and high temperature behaviors. In the low temperature range (i.e., below 30 degrees C) the rate constants do not change, suggesting that a superexchange mechanism is the modus operandi. In the high temperature range (i.e., >30 degrees C) the rate constants increase. Moreover, we find rather strong distance dependence for 1 and 2 and weak distance dependence for 2 and 3. A damping factor of 0.145 angstrom(-1) is derived for the former pair and 0.012 angstrom(-1) for the latter.

  DOI：

  10.1021/ja401239r

文献信息

• Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes
  作者：José L. Zafra、Agustín Molina Ontoria、Paula Mayorga Burrezo、Miriam Peña-Alvarez、Marek Samoc、Janusz Szeremeta、Francisco J. Ramírez、Matthew D. Lovander、Christopher J. Droske、Ted M. Pappenfus、Luis Echegoyen、Juan T. López Navarrete、Nazario Martín、Juan Casado

  DOI：10.1021/jacs.6b12520

  日期：2017.3.1

  delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both "intermolecular" excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which

  已经制备了具有供体-供体、受体-受体或供体-受体部分末端官能化并具有中心 [2.2] 对环烷单元的新型芪类和噻吩化合物，并根据通过键和通过空间 π 电子解释了它们的性质离域化（即 π 共轭）。基于光物理数据，它们的激发态特性已被描述，重点是中心 [2.2] 对环芳烷参与与侧臂中的键共轭竞争。为此，已经记录了作为温度、溶剂极性和固态压力的函数的双光子和单光子吸收和发射光谱。此外，通过 [2.2] 对环烷在中性状态和氧化物质（自由基阳离子，dications 和激进的 trications) 已经被研究，允许阐明通过空间电荷离域的振动拉曼指纹。因此，显示了 [2.2] 对环芳烷分子中“分子间”激发和电荷离域的互补方法，可用作有机半导体中电荷和激子迁移的模型。
• Utilization of Sc₃N@C₈₀in long-range charge transfer reactions
  作者：Silke Wolfrum、Julio R. Pinzón、Agustin Molina-Ontoria、Andreas Gouloumis、Nazario Martín、Luis Echegoyen、Dirk M. Guldi

  DOI：10.1039/c0cc04159a

  日期：——

  Electron accepting Sc3N@C80 promotes long-range charge transfer events evolving from photoexcited metalloporphyrins to afford radical ion pair states with lifetimes in the range of μs.

  接受电子的 Sc3N@C80 可促进从光激发金属卟啉演化出的长程电荷转移事件，从而产生寿命在 μs 范围内的自由基离子对状态。
• [2,2′]Paracyclophane-Based <i>π</i>-Conjugated Molecular Wires Reveal Molecular-Junction Behavior
  作者：Agustín Molina-Ontoria、Mateusz Wielopolski、Julian Gebhardt、Andreas Gouloumis、Timothy Clark、Dirk M. Guldi、Nazario Martín

  DOI：10.1021/ja109745a

  日期：2011.3.2

  The electronic coupling as well as the attenuation factor (beta), which depends primarily on the nature of the molecular bridge and is used as a benchmark to test the molecular wire behavior, have been determined in a systematic study carried out on a series of ZnP/C(60) conjugates connected through a [2,2`]paracyclophane-oligophenylenevinylene (pCp-oPPV). The convergent synthesis involves a series of Horner-Emmons olefination reactions or double palladium-catalized Heck-type reactions. ZnP-pCp-C(60) conjugates were finally obtained by the 1,3-dipolar cycloaddition reaction of the in situ-generated azomethyne ylide containing the ZnP-pCp moiety to the [60]fullerene using Prato conditions. Experimental (UV-vis, fluorescence, transient absorption spectroscopy, and solution electrochemistry) and theoretical studies revealed that the pCps act as molecular junctions. If hole transfer is assumed to be the dominant charge transfer (CT) mechanism, CT is facilitated in one direction (from C(60) to ZnP via pCp) but disfavored in the other direction (from ZnP to C(60) via pCp).