bis(2-benzimidazolylmethyl) (2-pyridylmethyl)amine | 315680-69-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: bis(2-benzimidazolylmethyl) (2-pyridylmethyl)amine
• 英文别名: bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine；N,N-bis(1H-benzimidazol-2-ylmethyl)-1-pyridin-2-ylmethanamine
• CAS: 315680-69-4
• 化学式: C₂₂H₂₀N₆
• 分子量: 368.441
• InChiKey: CDUZSGJOWWYCPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  73.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  安替比林 、 europium(III) chloride hexahydrate 、 bis(2-benzimidazolylmethyl) (2-pyridylmethyl)amine 以 甲醇 为溶剂， 生成 [Eu(bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine)(antipyrine)Cl(H2O)2]Cl2(H2O)2
  参考文献：
  名称：

  Syntheses, Crystal Structures, and Luminescent Properties of Lanthanide Complexes with Tripodal Ligands Bearing Benzimidazole and Pyridine Groups

  摘要：

  Two tripodal ligands, bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L-1) and bis(2-pyridylmethyl)(2-benzimidazolylmethyl)amine (L-2), were synthesized. With the third chromophoric ligand antipyrine (Antipy), three series of lanthanide(III) complexes were prepared: [LnL(1)(Antipy)(3)](ClO4)(3) (series A), [LnL(1) (Antipy)Cl(H2O)(2)]Cl-2(H2O)(2) (series B), and [LnL(2)(NO3)(3)] (series C). The nitrate salt of the free ligand H2L1.(NO3)(2) and six complexes were structurally characterized: Pr(3+)A, Y-3+A, Eu3+B, Eu3+C, Gd3+C and Tb3+C, in which the two A and three C complexes are isomorphous. Crystallographic studies showed that tripodal ligands L-1 and L-2 exhibited a tripodal coordination mode and formed 1:1 complexes with all lanthanide metal ions. The coordination numbers of the lanthanide metal ions for the A, B, and C complexes were 7, 8, and 10, respectively. Conductivity studies on the B and C complexes in methanol showed that, in the former, the coordinated Cl- dissociated to give 3:1 electrolytes and, in the latter, two coordinated NO3- ions dissociated to give 2:1 electrolytes. Detailed photophysical studies have been performed on the free ligands and their Gd(III), Eu(III), and Tb(III) complexes in several solvents. The results show a wide range in the emission properties of the complexes, which could be rationalized in terms of the coordination situation, the (LC)-L-3 level of the complexes, and the subtle variations in the steric properties of the ligands. In particular the Eu(3+)A and Tb(3+)A complexes, in which the central metal ions were wholly coordinated by chromophoric ligands of one L-1 and three antipyrine molecules, had relatively higher emission quantum yields than their corresponding B and C complexes.

  DOI：

  10.1021/ic025799p
• 作为产物：
  描述：

  2-氯甲基吡啶盐酸盐 在 盐酸 、 氢氧化钾 、 potassium carbonate 作用下， 反应 90.0h， 生成 bis(2-benzimidazolylmethyl) (2-pyridylmethyl)amine
  参考文献：
  名称：

  Studies on lanthanide complexes of the tripodal ligand bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine. Crystal structures and luminescence properties †

  摘要：

  合成了一种含有苯并咪唑和吡啶两种发色团的新的不对称三元配体双(2-苯并咪唑基甲基)(2-吡啶基甲基)胺(L)，并合成了两个系列的镧系(III)配合物[LnL(NO3)3]-C2H5OH（Ln = La、Sm、Eu、Gd、Tb 或 Tm）和 [LnLCl3(H2O)]-C2H5OH（Ln = La、Sm、Eu、Tb 或 Ho）两个系列的镧系（III）配合物，并通过元素分析、FAB 质谱、1H NMR、电导率测量和红外光谱对其进行了表征。通过 X 射线衍射分析，确定了三种复合物 [SmL(NO3)3]-C2H5OH 1、[GdL(NO3)3]-C2H5OH 2 和 [SmLCl3(H2O)]-C2H5OH 3 的晶体和分子结构。1 和 2 是同构物，中心金属离子与配体的四个氮原子和三个螯合硝酸基团的六个氧原子配位。在复合物 3 中，除了配体的四个氮原子和三个氯原子外，还有一个 H2O 分子与之配位。对[LnL(NO3)3]-C2H5OH 复合物在甲醇中的电导率研究表明，其中两个硝酸根阴离子解离出 2∶1 的电解质。通过比较 Eu3+ 和 Tb3+ 复合物在 CH3OH 和 CD3OD 中的发射寿命，得出 q（配位的甲醇分子数）的平均值为 3.4，表明形成了 [LnL(NO3)(CH3OH)3][NO3]2 物种。在 MeCN 中进行的发光研究表明，硝酸盐共配位系列的发射量子产率大大高于氯化物系列。

  DOI：

  10.1039/b003566l

文献信息

• Tailored Ligand Acceleration of the Cu-Catalyzed Azide−Alkyne Cycloaddition Reaction: Practical and Mechanistic Implications
  作者：Stanislav I. Presolski、Vu Hong、So-Hye Cho、M.G. Finn

  DOI：10.1021/ja105743g

  日期：2010.10.20

  components were prepared for ligand acceleration of the copper-catalyzed azide-alkyne cycloaddition reaction. Two classes of ligands were identified: those that give rise to high reaction rates in coordinating solvents but inhibit the process when used in excess relative to copper and those that provide for fast catalysis in water and are not inhibitory in excess. Several "mixed" ligands were identified that

  制备了含有 1,2,3-三唑基、2-苯并咪唑基和 2-吡啶基组分混合物的三（杂环甲基）胺，用于加速铜催化叠氮化物-炔烃环加成反应的配体加速。确定了两类配体：那些在配位溶剂中产生高反应速率但在相对于铜过量使用时抑制该过程的那些，以及在水中提供快速催化且不过量抑制的那些。鉴定了几种“混合”配体，它们在两种类型的条件下都表现良好。动力学测量作为配体：金属比率和催化剂浓度的函数被发现与活性 Cu(2)L 配方一致。由于强结合螯合剂并不总是最有效的，达到最佳速率需要评估反应混合物中的潜在供体分子。提供了简单的规则来指导用户选择有效的配体和反应条件，以适应大多数类型的底物、溶剂和浓度。
• Synthesis and properties of dinuclear iron-oxo complexes with tetradentate tripodal ligands
  作者：Yuzo Nishida、Miyuki Nasu、Tadashi Tokii

  DOI：10.1016/s0020-1693(00)80508-3

  日期：1990.3
• Nishida, Yuzo; Nasu, Miyuki; Tokii, Tadashi, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1990, vol. 45, # 7, p. 1093 - 1096
  作者：Nishida, Yuzo、Nasu, Miyuki、Tokii, Tadashi

  DOI：——

  日期：——
• Studies on lanthanide complexes of the tripodal ligand bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine. Crystal structures and luminescence properties †
  作者：Xiao-Ping Yang、Cheng-Yong Su、Bei-Sheng Kang、Xiao-Long Feng、Wang-Leng Xiao、Han-Qin Liu

  DOI：10.1039/b003566l

  日期：——

  A new unsymmetric tripodal ligand bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L) bearing two kinds of chromophores benzimidazole and pyridine has been synthesized, and two series of lanthanide(III) complexes [LnL(NO3)3]·C2H5OH (Ln = La, Sm, Eu, Gd, Tb or Tm) and [LnLCl3(H2O)]·C2H5OH (Ln = La, Sm, Eu, Tb or Ho) have been characterized by elemental analyses, FAB mass spectra, 1H NMR, conductivity measurements, and IR spectra. The crystal and molecular structures of the three complexes [SmL(NO3)3]·C2H5OH 1, [GdL(NO3)3]·C2H5OH 2, and [SmLCl3(H2O)]·C2H5OH 3 have been determined by X-ray diffraction analysis. 1 and 2 are isomorphous with the central metal ion co-ordinated by the four nitrogen atoms of the ligand and six oxygen atoms of three chelating nitrate groups. In complex 3, besides the four nitrogen atoms of the ligand and three chlorine atoms, there is one H2O molecule co-ordinated. Conductivity studies on the [LnL(NO3)3]·C2H5OH complexes in methanol showed that two of the nitrate anions dissociate to give 2∶1 electrolytes. Comparison of the emission lifetimes of the Eu3+ and Tb3+ complexes in CH3OH and CD3OD gives the average value for q, the number of co-ordinated methanol molecules, of 3.4, suggesting the formation of species [LnL(NO3)(CH3OH)3][NO3]2. The emission quantum yields of the nitrate-co-ordinated series are substantially higher than those of the chloride series, as shown by luminescence studies in MeCN.

  合成了一种含有苯并咪唑和吡啶两种发色团的新的不对称三元配体双(2-苯并咪唑基甲基)(2-吡啶基甲基)胺(L)，并合成了两个系列的镧系(III)配合物[LnL(NO3)3]-C2H5OH（Ln = La、Sm、Eu、Gd、Tb 或 Tm）和 [LnLCl3(H2O)]-C2H5OH（Ln = La、Sm、Eu、Tb 或 Ho）两个系列的镧系（III）配合物，并通过元素分析、FAB 质谱、1H NMR、电导率测量和红外光谱对其进行了表征。通过 X 射线衍射分析，确定了三种复合物 [SmL(NO3)3]-C2H5OH 1、[GdL(NO3)3]-C2H5OH 2 和 [SmLCl3(H2O)]-C2H5OH 3 的晶体和分子结构。1 和 2 是同构物，中心金属离子与配体的四个氮原子和三个螯合硝酸基团的六个氧原子配位。在复合物 3 中，除了配体的四个氮原子和三个氯原子外，还有一个 H2O 分子与之配位。对[LnL(NO3)3]-C2H5OH 复合物在甲醇中的电导率研究表明，其中两个硝酸根阴离子解离出 2∶1 的电解质。通过比较 Eu3+ 和 Tb3+ 复合物在 CH3OH 和 CD3OD 中的发射寿命，得出 q（配位的甲醇分子数）的平均值为 3.4，表明形成了 [LnL(NO3)(CH3OH)3][NO3]2 物种。在 MeCN 中进行的发光研究表明，硝酸盐共配位系列的发射量子产率大大高于氯化物系列。
• Syntheses, Crystal Structures, and Luminescent Properties of Lanthanide Complexes with Tripodal Ligands Bearing Benzimidazole and Pyridine Groups
  作者：Xiao-Ping Yang、Bei-Sheng Kang、Wai-Kwok Wong、Cheng-Yong Su、Han-Qin Liu

  DOI：10.1021/ic025799p

  日期：2003.1.1

  Two tripodal ligands, bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L-1) and bis(2-pyridylmethyl)(2-benzimidazolylmethyl)amine (L-2), were synthesized. With the third chromophoric ligand antipyrine (Antipy), three series of lanthanide(III) complexes were prepared: [LnL(1)(Antipy)(3)](ClO4)(3) (series A), [LnL(1) (Antipy)Cl(H2O)(2)]Cl-2(H2O)(2) (series B), and [LnL(2)(NO3)(3)] (series C). The nitrate salt of the free ligand H2L1.(NO3)(2) and six complexes were structurally characterized: Pr(3+)A, Y-3+A, Eu3+B, Eu3+C, Gd3+C and Tb3+C, in which the two A and three C complexes are isomorphous. Crystallographic studies showed that tripodal ligands L-1 and L-2 exhibited a tripodal coordination mode and formed 1:1 complexes with all lanthanide metal ions. The coordination numbers of the lanthanide metal ions for the A, B, and C complexes were 7, 8, and 10, respectively. Conductivity studies on the B and C complexes in methanol showed that, in the former, the coordinated Cl- dissociated to give 3:1 electrolytes and, in the latter, two coordinated NO3- ions dissociated to give 2:1 electrolytes. Detailed photophysical studies have been performed on the free ligands and their Gd(III), Eu(III), and Tb(III) complexes in several solvents. The results show a wide range in the emission properties of the complexes, which could be rationalized in terms of the coordination situation, the (LC)-L-3 level of the complexes, and the subtle variations in the steric properties of the ligands. In particular the Eu(3+)A and Tb(3+)A complexes, in which the central metal ions were wholly coordinated by chromophoric ligands of one L-1 and three antipyrine molecules, had relatively higher emission quantum yields than their corresponding B and C complexes.