4-[2-[4-(dimethylamino)phenyl]-4,8-bis(2-phenylethynyl)-[1,3]oxazolo[5,4-f][1,3]benzoxazol-6-yl]-N,N-dimethylaniline | 1350803-82-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4-[2-[4-(dimethylamino)phenyl]-4,8-bis(2-phenylethynyl)-[1,3]oxazolo[5,4-f][1,3]benzoxazol-6-yl]-N,N-dimethylaniline
• CAS: 1350803-82-5
• 化学式: C₄₀H₃₀N₄O₂
• 分子量: 598.704
• InChiKey: JGFLADRYBMGYDM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  46
• 可旋转键数：
  8
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  58.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4-二甲氨基苯甲酸 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 磷酸 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 27.0h， 生成 4-[2-[4-(dimethylamino)phenyl]-4,8-bis(2-phenylethynyl)-[1,3]oxazolo[5,4-f][1,3]benzoxazol-6-yl]-N,N-dimethylaniline
  参考文献：
  名称：

  Benzobisoxazole Cruciforms: Heterocyclic Fluorophores with Spatially Separated Frontier Molecular Orbitals

  摘要：

  We report the,synthesis of nine conjugated cruciform-shaped molecules based: on the central benzo[1,2-d:4,5-d']bisoxazole nucleus, at Which two conjugated currents intersect at a 90 angle. Cruciforms' substituents were varied pairwise among the electron-neutral phenyl groups, electron-rich 4-(N,N-dimethylamino)phenyl substituents, and electron-poor pyridines. Hybrid density functional theory calculations revealed that the highest occupied molecular orbitals (HOMOs) are localized (24-99%) in all cruciforms, in contrast to the lowest unoccupied molecular orbitals (LUMOs) which are strongly dependent on the substitution and less localized (6-64%). Localization of frontier molecular orbitals (FMOs) along different axes of these cruciforms makes them promising as sensing platforms, since analyte binding to the cruciform should mandate a change in the HOMO-LUMO gap and the resultant. optical properties. This prediction was verified using UV/vis absorption and emission spectroscopy cruciforms' protonation results in hypsochromic and bathochromic shifts consistent with the preferential stabilization of HOMO and LUMO, respectively. In donor-acceptor-substituted systems, a two-step optical response to protonation was observed,wherein an initial bathochromic shifts is followed by a hypsochromic one with continued acidification. X-ray diffraction studies of three selected cruciforms revealed the expected similar to 90 degrees angle between the cruciform's substituents, and crystal packing patterns dominated by [pi...pi] stacking and edge-to-face [C-H center dot center dot center dot pi] contacts.

  DOI：

  10.1021/jo202107w

文献信息

• Benzobisoxazole Cruciforms: Heterocyclic Fluorophores with Spatially Separated Frontier Molecular Orbitals
  作者：Jaebum Lim、Thomas A. Albright、Benjamin R. Martin、Ognjen Š. Miljanić

  DOI：10.1021/jo202107w

  日期：2011.12.16

  We report the,synthesis of nine conjugated cruciform-shaped molecules based: on the central benzo[1,2-d:4,5-d']bisoxazole nucleus, at Which two conjugated currents intersect at a 90 angle. Cruciforms' substituents were varied pairwise among the electron-neutral phenyl groups, electron-rich 4-(N,N-dimethylamino)phenyl substituents, and electron-poor pyridines. Hybrid density functional theory calculations revealed that the highest occupied molecular orbitals (HOMOs) are localized (24-99%) in all cruciforms, in contrast to the lowest unoccupied molecular orbitals (LUMOs) which are strongly dependent on the substitution and less localized (6-64%). Localization of frontier molecular orbitals (FMOs) along different axes of these cruciforms makes them promising as sensing platforms, since analyte binding to the cruciform should mandate a change in the HOMO-LUMO gap and the resultant. optical properties. This prediction was verified using UV/vis absorption and emission spectroscopy cruciforms' protonation results in hypsochromic and bathochromic shifts consistent with the preferential stabilization of HOMO and LUMO, respectively. In donor-acceptor-substituted systems, a two-step optical response to protonation was observed,wherein an initial bathochromic shifts is followed by a hypsochromic one with continued acidification. X-ray diffraction studies of three selected cruciforms revealed the expected similar to 90 degrees angle between the cruciform's substituents, and crystal packing patterns dominated by [pi...pi] stacking and edge-to-face [C-H center dot center dot center dot pi] contacts.