二(1-乙基-2-[(6'-羧基)吡啶-2'-基]苯并咪唑-5-基)-甲烷 | 218461-49-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 中文名称: 二(1-乙基-2-[(6'-羧基)吡啶-2'-基]苯并咪唑-5-基)-甲烷
• 英文名称: bis(1-ethyl-2-[(6'-carboxy)pyridin-2'-yl]benzimidazol-5-yl)-methane
• 英文别名: bis(1-ethyl-2-[(6'-carboxy)pyridin-2'-yl]benzimidazol-5-yl)methane；bis{1-ethyl-2-[(6'-carboxy)pyridin-2'-yl]benzimidazol-5-yl}methane；6-[5-[[2-(6-Carboxypyridin-2-yl)-1-ethylbenzimidazol-5-yl]methyl]-1-ethylbenzimidazol-2-yl]pyridine-2-carboxylic acid
• CAS: 218461-49-5
• 化学式: C₃₁H₂₆N₆O₄
• 分子量: 546.585
• InChiKey: XERBCJFQRBGDIV-UHFFFAOYSA-N

物化性质

• 沸点：
  887.7±75.0 °C(Predicted)
• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  41
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  136
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  二(1-乙基-2-[(6'-羧基)吡啶-2'-基]苯并咪唑-5-基)-甲烷 在 氯化亚砜 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  线性四金属三链镧系镧系元素的预测，合成策略和分离。

  摘要：

  DOI：

  10.1002/anie.200503040
• 作为产物：
  描述：

  bis{1-ethyl-2-[6'-(N,N-diethylcarbamoyl)pyridini-2'-yl]benzimidazol-5-yl}methane 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以93.5%的产率得到二(1-乙基-2-[(6'-羧基)吡啶-2'-基]苯并咪唑-5-基)-甲烷
  参考文献：
  名称：

  Lanthanide Helicates Self-Assembled in Water:  A New Class of Highly Stable and Luminescent Dimetallic Carboxylates

  摘要：

  The segmental ligand bis{1-ethyl-2-[6'-carboxy)pyridin-2'-yl]benzimidazol-5-yl}methane (L-C) reacts with the entire series of Ln(III) ions to yield a new class of neutral lanthanide carboxylates, the triple-stranded dimetallic helicates [Ln(2)(L-C-2H)(3)], which are stable in water in the pH range 4-13. A competitive titration with 1,4,7,10-tetraazacyclododecane-N,N',N",N'''-tetraacetic acid (dota) shows the Eu-III helicate to have a stability comparable to that of [Eu(dota)](-). According to the X-ray structures of isotypical [Ln(2)(L-C-2H)(3)].20.5H(2)O (Ln = Eu, Tb) (C(93)H(72)Ln(2)N(18)O(12).20.5H(2)O, monoclinic, P2(1)/c, Z = 8), the helicates are comprised of two types of slightly different molecules (A, B) within the asymmetric unit. The three ligand strands are helically wrapped around the two nine-coordinate Ln(III) ions, leading to pseudo-D-3 symmetries around the metals. The Ln(III) distances lie in the ranges 8.81--8.83 Angstrom for molecules A and 9.04-9.07 Angstrom for molecules B, while the helical pitch amounts to 23.7--23.8 Angstrom (A) and 24.5-24.7 Angstrom (B). In solution, the helicates retain time-averaged D-3 symmetries along the entire Ln(III) series, as shown by H-1 and C-13 NMR. The derivation of equations adapted to heterodimetallic complexes allows the separation of contact and dipolar contributions to the isotropic paramagnetic shift. Somewhat different structures are evidenced between larger (Ln = Ce-Tb) and smaller (Ln = Er--Yb) Ln(III) ions, attributed to a lengthening of the helix on going toward heavier lanthanides. The photophysical properties of the helicates depend on the nature of the Ln(III) ion, and LC is revealed to be a good sensitizer of Eu-III. The flexible route used to synthesize LC opens interesting perspectives for the fine-tuning of the chemical and photophysical properties of lanthanide-containing homodimetallic helicates with potential applications in labeling and sensing technologies.

  DOI：

  10.1021/ja991854q

文献信息

• Lanthanide Homobimetallic Triple‐Stranded Helicates: Insight into the Self‐Assembly Mechanism
  作者：Mourad Elhabiri、Josef Hamacek、Jean‐Claude G. Bünzli、Anne‐Marie Albrecht‐Gary

  DOI：10.1002/ejic.200300549

  日期：2004.1

  The self-assembly mechanism leading to the exclusive formation of a triple-stranded bimetallic helicate upon reaction of Eu III with a ditopic hexadentate ligand L bearing two carboxylate moieties has been fully elucidated in water for a wide range of [Eu]tot/[L]tot ratios. Using a fruitful combination of electrospray mass spectrometry, potentiometry, UV/Vis spectrophotometry, luminescence, and 1 H

  在 Eu III 与带有两个羧酸盐部分的双位六齿配体 L 反应后，导致独家形成三链双金属螺旋的自组装机制已经在水中得到了广泛的 [Eu]tot/[L] ]总比率。使用电喷雾质谱、电位测定、紫外/可见分光光度法、发光和 1 H NMR 光谱的卓有成效的组合，最终产物 Eu2L3 和中间物种 EuL2 和 Eu2L2 已被表征。与与类似中性配体形成的相应配合物相比，L 中末端羧酸盐的存在显着降低了 Eu2L2 和 Eu2L3 中配位位点的静电排斥，从而增加了 L-铕 (III) 配合物的稳定性。
• The first lanthanide-containing helicates self-assembled in water
  作者：Mourad Elhabiri、Rosario Scopelliti、Jean-Claude G. Bünzli、Claude Piguet

  DOI：10.1039/a806730i

  日期：——

  Triple-stranded bimetallic helicates [Ln2(LC –2H)3] form in water by a strict self-assembly process and are shown to be thermodynamically very stable (log β23 > 26) and luminescent (Ln = Eu).

  三链双金属螺旋体[Ln2(LC -2H)3]在水中通过严格的自组装过程形成，并被证明在热力学上非常稳定（log β23 > 26）和发光（Ln = Eu）。
• Visible and Near-Infrared Luminescence of Lanthanide-Containing Dimetallic Triple-Stranded Helicates:  Energy Transfer Mechanisms in the Sm^III and Yb^III Molecular Edifices
  作者：Fabiana R. Gonçalves e Silva、Oscar L. Malta、Christine Reinhard、Hans-Ulrich Güdel、Claude Piguet、Jacques E. Moser、Jean-Claude G. Bünzli

  DOI：10.1021/jp012884u

  日期：2002.3.1

  The photophysical properties of the triple-stranded dimetallic helicates [Ln(2)(L-C-2H)(3)].H2O (Ln = Nd, Sm, Dy, Yb) are determined in water and D2O Solutions, and energy transfer processes are modeled for Sm-III. The luminescence of Nd-III, SMIII, and Yb-III is sensitized by (L-C-2H)(2-), but the energy transfer from the ligand to the Ln(III) ions is not complete, resulting in residual ligand emission. The luminescence of the Nd-III helicate is very weak due to nonradiative de-excitation processes. On the other hand, the WIT and Sm-III helicates exhibit fair quantum yields, 1.8% and 1.1% in deuterated water, respectively. The energy transfer rates between (L-C-2H)(2-) and Sm-III levels are calculated by direct and exchange Coulomb interaction models. This theoretical modeling coupled to numerical solutions of the rate equations leads to an estimate of the emission quantum yields in H2O and D2O, which compares favorably with experimental data. The main component of the ligand-to-metal energy transfer (97.5%) goes through a 3pipi* --> (5)G(5/2)((1)) path, and the operative mechanism is of the exchange type, For the Yb-III helicate, minor effects of oxygen on the sensitization of Yb-III and nanosecond time-resolved spectroscopy point to the energy transfer mechanism being consistent with a recently proposed pathway involving fast electron transfer and Yb-II. No up-conversion process could be identified. Ligand-field splitting of the F-2(5/2) (3E(1/2) + E-3/2) and F-2(7/2) (2E(1/2) + E-3/2) levels of Yb-III is consistent with D-3 symmetry.