1-trimethylsilylethynyl-N,N’-bis(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic diimide | 1174418-74-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 1-trimethylsilylethynyl-N,N’-bis(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic diimide
• CAS: 1174418-74-6
• 化学式: C₅₅H₇₀N₂O₄Si
• 分子量: 851.257
• InChiKey: DEPCLSHJJFZLQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.78
• 重原子数：
  62.0
• 可旋转键数：
  22.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  74.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-trimethylsilylethynyl-N,N’-bis(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic diimide 在 copper(l) iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以70%的产率得到bis[1-ethynyl-N,N'-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxaylic diimide]
  参考文献：
  名称：

  Structural Refinement of Ladder-Type Perylenediimide Dimers: A Classical Tale of Conformational Dynamics

  摘要：

  We have synthesized and thoroughly characterized two representative ladder-type acetylene-bridged perylenediimide dimers bearing long alkyl chain solubilizing groups, bis[1-ethynyl-N,N'-bis (1-hexylheptyl)-perylene-3,4:9,10-tetra-carboxylic diimide] ([PDICC](2), 1) and 1,1'-ethynyl-bis[N,N'-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide] ([PDI](2)CC, 2). In these dimeric PDI molecules, NMR-based structural characterization became nontrivial because severe H-1 spectral broadening and greater than expected numbers of observed C-13 resonances substantially complicated the interpretation of traditional 1-D spectra. However, rational two-dimensional NMR approaches based on both homo- and heteronuclear couplings (H-1-H-1 COSY; H-1-C-13 HSQC), in conjunction with high-level structural DFT calculations (GIAO/B3LYP/6-31G(d,p)/PCM, chloroform), were readily applied to these structures, producing well-defined analytical characterization, and the associated methodology is described in detail. Furthermore, on the basis of dynamic NMR experiments, both 1 and 2 were found to exist in a perylene-centered conformational dynamic equilibrium (Delta G double dagger = 13-17 kcal/mol), which primarily caused the observed ambiguities in conventional 1-D spectra.

  DOI：

  10.1021/jo401348w
• 作为产物：
  描述：

  2,9-二(1-己基庚基)-蒽并[2,1,9-def:6,5,10-d'e'f']二异喹啉-1,3,8,10(2H,9H)-四酮 在 copper(l) iodide 、 四(三苯基膦)钯 、 溴 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 120.0h， 生成 1-trimethylsilylethynyl-N,N’-bis(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic diimide
  参考文献：
  名称：

  Structural Refinement of Ladder-Type Perylenediimide Dimers: A Classical Tale of Conformational Dynamics

  摘要：

  We have synthesized and thoroughly characterized two representative ladder-type acetylene-bridged perylenediimide dimers bearing long alkyl chain solubilizing groups, bis[1-ethynyl-N,N'-bis (1-hexylheptyl)-perylene-3,4:9,10-tetra-carboxylic diimide] ([PDICC](2), 1) and 1,1'-ethynyl-bis[N,N'-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide] ([PDI](2)CC, 2). In these dimeric PDI molecules, NMR-based structural characterization became nontrivial because severe H-1 spectral broadening and greater than expected numbers of observed C-13 resonances substantially complicated the interpretation of traditional 1-D spectra. However, rational two-dimensional NMR approaches based on both homo- and heteronuclear couplings (H-1-H-1 COSY; H-1-C-13 HSQC), in conjunction with high-level structural DFT calculations (GIAO/B3LYP/6-31G(d,p)/PCM, chloroform), were readily applied to these structures, producing well-defined analytical characterization, and the associated methodology is described in detail. Furthermore, on the basis of dynamic NMR experiments, both 1 and 2 were found to exist in a perylene-centered conformational dynamic equilibrium (Delta G double dagger = 13-17 kcal/mol), which primarily caused the observed ambiguities in conventional 1-D spectra.

  DOI：

  10.1021/jo401348w

文献信息

• Conjugated Dimeric and Trimeric Perylenediimide Oligomers
  作者：Qifan Yan、Dahui Zhao

  DOI：10.1021/ol9012734

  日期：2009.8.6

  conjugatively linked by phenylene, ethynylene, or a butadiynylene spacer via the bay positions were prepared. Electrochemical and photophysical characterizations showed that oligomers connected by C−C triple bond(s) exhibited effectively lowered LUMO compared to the monomer. Molecular modeling confirmed that the C−C triple bond realized efficient delocalization of frontier orbitals, while phenylene was less competent

  制备了包括per二酰亚胺单元的二聚和三聚分子，所述per二酰亚胺单元通过亚乙基，亚乙炔基或丁二亚炔基间隔物经由间隔位置共轭连接。电化学和光物理特征表明，与单体相比，通过C-C三键连接的低聚物可有效降低LUMO。分子建模证实，CC三键实现了边界轨道的有效离域，而亚苯基在扩展共轭方面的能力较弱，这部分是由于空间相互作用所致。