HaaiMe | 93937-86-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: HaaiMe
• 英文别名: (E)-1-methyl-2-(phenylazo)imidazole；N(1)-methyl-2-(phenylazo)imidazole；(E)-1-methyl-2-phenylazoimidazole；E-1-methyl-2-(phenylazo)imidazole；1-methyl-2-(phenylazo)imidazole；1-methyl-2-phenylazoimidazole
• CAS: 93937-86-1
• 化学式: C₁₀H₁₀N₄
• 分子量: 186.216
• InChiKey: FLAQUJIURZWQSH-OUKQBFOZSA-N

物化性质

• 沸点：
  333.5±25.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  42.54
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  HaaiMe 以 乙腈 为溶剂， 生成 (Z)-1-methyl-2-(phenylazo)imidazole
  参考文献：
  名称：

  2-芳基偶氮咪唑在可见光下的光异构化：确定预测工具来预测和调整可能的光开关性能和顺式半衰期

  摘要：

  偶氮吡唑是一类新兴的光开关，而类似的基于偶氮咪唑的开关由于其顺式半衰期短、顺反光回复产率差以及有毒的紫外线（UV）光辅助异构化而无法引起太多关注。合成了一系列 24 种芳基取代的N-甲基-2-芳基偶氮咪唑，并从实验和理论上深入研究了它们的光开关性能和顺反异构化动力学。对位-π-供体取代的偶氮咪唑具有高度扭曲的T形顺式构象，显示出几乎完全的双向光开关，而二-o-取代的开关表现出非常长的顺式半衰期（天-年），具有近乎理想的 T 形构象。这项研究展示了芳环中的电子密度如何通过扭转 NNAr 二面角来影响顺式半衰期和顺反光复归，这可以用作预测指标，用于设想和调整任何可能的开关性能和半衰期。给予2-芳基偶氮咪唑。通过应用该工具，设计了两种性能更好的偶氮咪唑光电开关。所有开关均允许紫光（400-405 nm）和橙光（>585 nm）照射分别进行正向和反向异构化，并表现出相对较高的量子产率和令人印象深刻的抗光漂白性。

  DOI：

  10.1021/acs.joc.3c00211
• 作为产物：
  描述：

  (Z)-1-methyl-2-(phenylazo)imidazole 以 氘代乙腈 为溶剂， 生成 HaaiMe
  参考文献：
  名称：

  通过杂芳基设计调整偶氮杂芳烃光开关性能

  摘要：

  光可切换化合物可以通过光在两种异构体之间可逆地切换，继续引起广泛应用的显着关注。偶氮杂芳烃代表了一种相对较新但研究不足的光开关类型，其中传统偶氮苯类中的一个芳环已被五元杂芳环取代。初步研究表明，偶氮杂芳烃——特别是芳基并吡唑——具有优异的光开关特性（定量开关和长 Z 异构体半衰期）。在这里，我们提出了一项系统的计算和实验研究，以阐明芳基并吡唑的长热半衰期和优异的可寻址性的起源，并应用这一理解来确定各种可比较的偶氮杂芳基光开关的重要结构-性质关系。我们通过杂环的调节，鉴定了具有 Z 异构体半衰期从几秒到几小时、到几天甚至几年以及可变吸收特性的化合物。构象可能在决定这些性质方面发挥着最大的作用：异构化半衰期最长的化合物采用 T 形基态 Z 异构体构象并通过 T 形异构化途径进行，而对于具有最长异构化半衰期的化合物，实现了最完整的光开关具有扭曲（而不是 T 形）的 Z 异构体构象。通过平衡这些因素，我们报告了一种新的偶氮吡唑

  DOI：

  10.1021/jacs.6b11626

文献信息

• Cadmium(II) Complexes of (Arylazo)imidazoles:  Synthesis, Structure, Photochromism, and Density Functional Theory Calculation
  作者：K. K. Sarker、D. Sardar、K. Suwa、J. Otsuki、C. Sinha

  DOI：10.1021/ic7012073

  日期：2007.10.1

  azoimidazole. The reverse transformation, cis-to-trans, is very slow with visible light irradiation. Quantum yields (phit-->c) of trans-to-cis isomerization are calculated, and the free ligand shows higher phi values than their cadmium(II) iodo complexes. The cis-to-trans isomerization is a thermally induced process. The activation energy (Ea) of cis-to-trans isomerization is calculated by a controlled-temperature

  CdX2与1-烷基-2-（苯基偶氮）咪唑（RaaiR'）之间的反应分离出组成为Cd（RaaiR'）2X2的MeOH或MeCN络合物。从N，N-二甲基甲酰胺（DMF）结晶Cd（RaaiR'）2I2已分离[Cd（RaaiR'）I2.DMF]，而Cd（RaaiR'）2X2（X = Cl和Br）在其组成上保持不变在相同条件下结晶。该结构是通过光谱数据（紫外可见和1H NMR）确定的，在后一种情况下，通过对[Cd（TaiMe）I2.DMF]进行单晶X射线衍射研究来证实[其中TaiMe = 1-甲基- 2-（对甲苯基）咪唑]。Cd（RaaiR'）2I2和[Cd（RaaiR'）I2.DMF]的MeCN溶液中的紫外线照射显示了配位偶氮咪唑的反式-顺式异构化。在可见光照射下，顺式至反式的反向转化非常缓慢。计算了反式-顺式异构化的量子产率（phit-> c），并且游离配体比其镉（II）碘配合物显示出更高的ph
• Structure, electrochemistry and photochromism of [Cu(RaaiR′)(PPh3)X] (RaaiR′=1-alkyl-2-(arylazo)imidazole; X=Cl, Br, I) and correlation with theoretical calculations
  作者：Gunomoni Saha、Kamal Krishna Sarkar、Dibakar Sardar、Jack Cheng、Tian-Huey Lu、Chittaranjan Sinha

  DOI：10.1016/j.poly.2012.07.039

  日期：2012.9

  The reaction between CuX (X = Cl, Br, I), PPh3 and 1-alkyl-2-(arylazo)imidazole (RaaiR') has synthesized [Cu(RaaiR')(PPh3)X]. The composition has been established by spectroscopic (UV-Vis, IR, H-1 NMR) data and the single crystal X-ray diffraction study of [Cu(MeaaiH)(PPh3)Cl] and [Cu(MeaaiH)(PPh3)Br] (MeaaiH = 2-(p-tolylazo)imidazole) have confirmed the structures. These complexes show trans-to-cis (E-to-Z) photoisomerisation upon UV light irradiation. Quantum yields (phi(E -> Z)) of [Cu(RaaiR')(PPh3)X] are lower than the free ligand values. The rate of isomerisation follows the sequence [Cu(RaaiR')(PPh3)Cl] < [Cu(RaaiR')(PPh3)Br] < [Cu(RaaiR')(PPh3)I]. The cis-to-trans (Z-to-E) isomerisation is very slow upon light irradiation and has been achieved by a thermal route. The activation energy (E-a) of the Z-to-E isomerisation has been calculated by a controlled temperature reaction. OFT calculations of the optimized geometry of representative complexes have been used to determine the composition and energy of the molecular levels. (C) 2012 Elsevier Ltd. All rights reserved.
• Chowdhury, Bharati; Naskar, Kaushik; Mallick, Debashis, Journal of the Indian Chemical Society, 2018, vol. 95, # 4, p. 405 - 416
  作者：Chowdhury, Bharati、Naskar, Kaushik、Mallick, Debashis、Sen, Chandana、Sarkar, Kamal Krishna、Sinha, Chittaranjan

  DOI：——

  日期：——
• Misra, Tarun Kumar; Sinha, Chittaranjan, Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1999, vol. 38, # 4, p. 346 - 349
  作者：Misra, Tarun Kumar、Sinha, Chittaranjan

  DOI：——

  日期：——
• Palladium(II)-iodo-{1-alkyl-2-(arylazo)imidazole} complexes: Synthesis, structure, dynamics of photochromism and DFT computation
  作者：Chandana Sen、Suman Roy、Tapan Kumar Mondal、Rajib Ghosh、Jahur A. Mondal、Dipak K. Palit、Chittaranjan Sinha

  DOI：10.1016/j.poly.2014.09.033

  日期：2015.1

  [Pd(Raai-CnH2n+1)(2)I)](2)[Pd2I6} (Raai-CnH2n+1 = 1-alkyl-2-(arylazo)imidazole) has been characterized by the spectral data (UV-Vis, FfIR, Mass, H-1 NMR). The single crystal X-ray structure of [Pd(Meaai-C2H5)(2)I](2) [Pd2I6] shows that one Meaai-C2H5 acts as monodentate N(imidazoly1) donor, while the other one is bidentate N(imidazolyl), N(azo) chelator; the charge is neutralized with [Pd2I6](2-) anion. UV light irradiation in DMF solution of the complexes show trans-to-cis isomerisation of Raai-CnH2n+1 about -N=N- bond. Quantum yields (phi(t -> c)) of trans-to-cis isomerisation of the complexes are lower than that of the free ligand data. This observation is consistent with femtosecond transient absorption results of [Pd(Haai-C10H21)(2)][Pd2I6], which suggest that the trans -> cis isomerization occurs in the monodentate azo-imidazole group and the bidentate azo-imidazole, because of chelation with Pd(II), does not exhibit photochromism. The isomerization proceeds with a time constant of similar to 1.0 ps in acetonitrile, 0.6 ps in methanol, and 1.7 ps in ethylene glycol, which are comparable to those the free azo-imidazole ligand. In contrast, the reverse transformation, i.e. ds-to-trans, is carried out by thermal process and the activation energy (E-a) of cis-to-trans isomerisation of the complexes is lower than that of free ligand. The spectral property and photochromic efficiency have been explained by DFT computation of optimized geometry of the complex. (C) 2014 Elsevier Ltd. All rights reserved.