3,3′-[benzene-1,4-diylidi(E)diazene-2,1-diyl]bis[1′,3′,3′- trimethylspiro(2H-1-benzopyran-2,2′-indoline)-6-yl] | 1449790-54-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 3,3′-[benzene-1,4-diylidi(E)diazene-2,1-diyl]bis[1′,3′,3′- trimethylspiro(2H-1-benzopyran-2,2′-indoline)-6-yl]
• 英文别名: 3,3'-[benzene-1,4-diylidi(E)diazene-2,1-diyl]bis[1',3',3'-trimethylspiro(2H-1-benzopyran-2,2'-indoline)-6-yl]；3,3′-[benzene-1,4-diylidi(E)diazene-2,1-diyl]bis[1′,3′,3′-trimethylspiro(2H-1-benzopyran-2,2′-indoline)-6-yl]
• CAS: 1449790-54-8
• 化学式: C₄₄H₄₀N₆O₂
• 分子量: 684.841
• InChiKey: CGEGKBLFDSPMHY-MLGMXDONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.58
• 重原子数：
  52.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  74.38
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为产物：
  描述：

  水杨醛 在 盐酸 、 sodium hydroxide 、 sodium nitrite 作用下， 以 氯仿 、 水 为溶剂， 反应 2.33h， 生成 3,3′-[benzene-1,4-diylidi(E)diazene-2,1-diyl]bis[1′,3′,3′- trimethylspiro(2H-1-benzopyran-2,2′-indoline)-6-yl]
  参考文献：
  名称：

  Development of molecular photoswitch with very fast photoresponse based on asymmetrical bis-azospiropyran

  摘要：

  To study the effects of an extended bis-azo conjugated bridge with two different photochemical functions on a molecule in photochromic responses, a novel asymmetrical bifunctional bis-azo spiropyran photochromic dye was designed and synthesized. The obtained photoresponses were compared with symmetrical bifunctional bis-azo spiropyran analogues, and relative mono-azo and simple spiropyrans. Colourimetric behaviour, luminescence, and switching kinetics of all the dyes were studied. The largest molar absorption coefficient in merocyanine form, quickest response to light, and highest fluorescence quantum yield of the spiropyran form with a superior ratio of emission intensities of spiropyran to merocyanine form were achieved for the asymmetric bis-azospiropyran. Solvatochromic effect was studied to observe the solvent effects on non-irradiation colouration of the photochromic dyes. Furthermore, The molecular energy levels for optimized geometries of the synthesized bis-azospiropyrans and their probable photochemical products were obtained at the B3LYP/6-31G(d) level of theory. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.saa.2015.07.110

文献信息

• Symmetric Bis-Azospiropyrans: Synthesis, Characterization and Colorimetric Study
  作者：Farahnaz Nourmohammadian、Ali Ashtiani Abdi

  DOI：10.5012/bkcs.2013.34.6.1727

  日期：2013.6.20

  Synthesis and characterization of some novel symmetric bis-azospiropyrans are reported in this study. These bis-azospiropyrans are bifunctional chromophores with two spiropyrans linked by a bis-azo extended aromatic system that produce more color strength (large molar absorption coefficient in mero forms) due to appending two azospiropyran chromophores on one molecule. Comparing to the molar absorption coefficients of the conventional spiropyran chromophores ($\varepsilon}=0.31\times}10^4\;M^-1}\cdot}cm^-1}$) and mono-azospiropyran chromophores ($1.35\times}10^4\;M^-1}\cdot}cm^-1}$), the novel synthesized photochromes showed astonishingly increased molar absorption coefficients ($2.3-3.8\times}10^4\;M^-1}\cdot}cm^-1}$) at the same conditions. Such high molar absorption coefficients confers high sensitivity to light and more color intensity of mero form, that leads to improvement of their light sensitivity and better discrimination of spiro (OFF) form from mero (ON) ones in molecular switches. The structures were deduced from their MS, FT-IR, and $^1H$-NMR spectroscopic data and CHN analysis. All the synthesized photochemically bifunctional compounds revealed fluorescent emission in their colorless form which was faded out after exposing to UV light. Fluorescence quantum yield values of the mero forms were 0.25-0.81 and two high fluorescence quantum yield values (0.60 and 0.81) were found in these series.

  本研究报告了一些新型对称双偶氮螺吡喃的合成与表征。这些双偶氮螺吡喃是具有双功能的染料，由通过双偶氮扩展芳香系统连接的两个螺吡喃构成，由于在一个分子上附加了两个偶氮螺吡喃染料，使其能够产生更强的颜色强度（亚甲基形式的大摩尔吸收系数）。与常规螺吡喃染料（$\varepsilon}=0.31\times}10^4\;M^-1}\cdot}cm^-1}$）和单偶氮螺吡喃染料（$1.35\times}10^4\;M^-1}\cdot}cm^-1}$）的摩尔吸收系数相比，合成的新型光致变色染料在相同条件下表现出惊人的摩尔吸收系数增加（$2.3-3.8\times}10^4\;M^-1}\cdot}cm^-1}$）。如此高的摩尔吸收系数赋予其对光的高灵敏性和亚甲基形式更强的颜色强度，这改善了其对光的敏感性，并在分子开关中更好地区分螺旋（关闭）形式与亚甲基（开启）形式。结构通过其质谱（MS）、傅里叶变换红外光谱（FT-IR）和$^1H$-核磁共振光谱数据以及CHN分析推断得出。所有合成的光化学双功能化合物在无色形式下均显示出荧光发射，且在暴露于紫外光后会逐渐褪色。亚甲基形式的荧光量子产率值为0.25-0.81，其中两个高荧光量子产率值（0.60和0.81）在该系列中被发现。