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 | 1269228-99-0

• 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'-(((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
• CAS: 1269228-99-0
• 化学式: C₇₄H₈₈O₆
• 分子量: 1073.51
• InChiKey: UGVNUWBAMPSMFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.71
• 重原子数：
  80.0
• 可旋转键数：
  34.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.38
• 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)-4,1-phenylene))bis(ethene-2,1-diyl))dibenzaldehyde 、 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.0h， 以43%的产率得到
  参考文献：
  名称：

  Utilization of Sc₃N@C₈₀in long-range charge transfer reactions

  摘要：

  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。

  DOI：

  10.1039/c0cc04159a
• 作为产物：
  描述：

  4,12-divinyl[2.2]paracyclophane 在 potassium tert-butylate 、 四丁基溴化铵 、 palladium diacetate 、 potassium carbonate 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 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：

  Utilization of Sc₃N@C₈₀in long-range charge transfer reactions

  摘要：

  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。

  DOI：

  10.1039/c0cc04159a

文献信息

• Blending Through-Space and Through-Bond π–π-Coupling in [2,2′]-Paracyclophane-oligophenylenevinylene Molecular Wires
  作者：Mateusz Wielopolski、Agustín Molina-Ontoria、Christina Schubert、Johannes T. Margraf、Evangelos Krokos、Johannes Kirschner、Andreas Gouloumis、Timothy Clark、Dirk M. Guldi、Nazario Martín

  DOI：10.1021/ja401239r

  日期：2013.7.17

  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.
• [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).