2,2′-bi [1,10] phenanthroline | 56376-69-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 2,2′-bi [1,10] phenanthroline
• 英文别名: 2,2'-Bi-1,10-phenanthroline；2-(1,10-phenanthrolin-2-yl)-1,10-phenanthroline
• CAS: 56376-69-3
• 化学式: C₂₄H₁₄N₄
• 分子量: 358.402
• InChiKey: AZQYARARSACUOS-UHFFFAOYSA-N

物化性质

• 熔点：
  >300 °C
• 沸点：
  642.0±50.0 °C(Predicted)
• 密度：
  1.357±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  28
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2′-bi [1,10] phenanthroline 、 europium(III) trifluoromethanesulfonate 以 甲醇 为溶剂， 以87%的产率得到[Eu(2,2'-bi-1,10-phenanthroline)2(trifluoromethanesulfonate)](trifluoromethanesulfonate)2*4H2O
  参考文献：
  名称：

  Eu(III) Complexes of Tetradentate Ligands Related to 2,9-Di(pyrid-2′-yl)-1,10-phenanthroline and 2,2′-Bi-1,10-phenanthroline

  摘要：

  A series of six tetradentate polypyridine-type ligands (L) have been used to prepare the corresponding Eu(III) complexes [Eu(L)(2)(S)(n+) (n = 2, 3) where S = H2O or CF3SO3-. Two of the ligands, 2,9-di(pyrid-2'-yl)-1,10-phenanthroline (4) and its dipyridophenazine analogue (6) are symmetrical around a central phenanthroline ring. The other four ligands are 2,2'-bi-1,10-phenanthroline and its 3,3'-di-, tri-, and tetramethylene-bridged analogues (5a-d) whose conformations are governed by the length of the polymethylene bridge. H-1 NMR and X-ray analysis indicate that all of the complexes have a C-2v symmetry. The biphenanthroline series shows a strong correlation of the conjugation between the two halves of the ligand, as governed by the bridge, with the absorption and emission properties of the Eu(III) complex. The complex having the most distorted, tetramethylene-bridged ligand exhibits a weak, high energy pi-pi* absorption and low sensitization efficiency. The luminescence decays are monoexponential for complexes of 4 and either monoexponential or biexponential for the complexes of 5 depending on its solution concentration and the length of the bridge. The complexes of 4 exhibit much longer lifetime, higher overall quantum yield, and higher sensitization efficiency than complexes of 5 while the complex of 6 emits very weakly. The Eu(D-5(0)) lifetime for [Eu(4)(2)(H2O)](ClO4)(3) is shorter than for [Eu(4)(2)(CF3SO3)](CF3SO3)(2), reflecting the effect of the coordinated water. The complexes are examined for stability in the presence of water and found to retain most of their luminescent properties even in the presence of a large excess of water.

  DOI：

  10.1021/ic100338t
• 作为产物：
  描述：

  2-氯-1,10-菲咯啉 在 锌 四乙基碘化铵 、 三苯基膦 、 nickel dichloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以71%的产率得到2,2′-bi [1,10] phenanthroline
  参考文献：
  名称：

  Syntheses, Spectroscopic Properties, and Cu(I) Complexes of All Possible Symmetric Bi-1,10-phenanthrolines

  摘要：

  All possible symmetric bi-1,10-phenanthrolines (biphens) were synthesized by Ni-catalyzed coupling of corresponding halo-1,10-phenanthrolines. Their absorption and emission spectra were compared with those of phenanthroline as the reference compound. The spectral feature is explained by the molecular conformation, namely, coplanar 2,2'- and 3,3'-biphens and nearly bisected 4,4'- and 5,5'-biphens. The effects of additives, H+ or Zn2+, on the electronic spectra varied depending on the biphen ligand. The 2,2'-ligand formed a helical complex with Cu+ ions in a 2:2 ratio as revealed by spectroscopic titration and X-Ray analysis.

  DOI：

  10.3987/com-04-10273

文献信息

• A broad view on the complexity involved in water oxidation catalysis based on Ru–bpn complexes
  作者：Abolfazl Ghaderian、Alicja Franke、Marcos Gil-Sepulcre、Jordi Benet-Buchholz、Antoni Llobet、Ivana Ivanović-Burmazović、Carolina Gimbert-Suriñach

  DOI：10.1039/d0dt03548c

  日期：——

  oxidation process (kdimer = 1.35 M−1 s−1), which is in line with the electrochemical data at pH = 7 (kdimer = 1.4 M−1 s−1). 34+ can be reduced to [Ru(bpn)(pic)(OH2)]2+ (42+), showing a sort of square mechanism. All species generated in situ at pH 7 have been thoroughly characterized by NMR, mass spectrometry, UV-Vis and electrochemical techniques. 12+ and 42+ are also characterized by single crystal X-ray

  具有式[Ru（bpn）（pic）2 ] Cl 2（其中bpn是2,2​​'-bi（1,10-菲咯啉），pic代表4- picoline）的新Ru配合物（1 Cl 2）为合成以研究涉及一类N4四齿赤道配体介导的电化学和化学水氧化的活性物质的真实性质。进行了全面的电化学（通过使用循环伏安法，微分脉冲伏安法和受控电势电解），结构化（X射线衍射分析），光谱学（UV-vis，NMR和共振拉曼光谱）以及动力学研究。1 2+发生化学反应时发生取代反应（通过使用NaIO 4）或用电化学方法将其氧化为Ru III，其中甲基吡啶被羟基配体取代，生成[Ru（bpn）（pic）（OH）] 2+（2 2+）。前一个配合物与氧桥化合物[Ru（bpn）（pic）] 2（μ-O）} 4+（3 4+）处于平衡状态，这是Ru III氧化态下配合物的主要形式。二聚体的形成是整个氧化过程的速率决定步骤（k二聚体= 1.35 M
• Fluorescence and Metal-Binding Properties of the Highly Preorganized Tetradentate Ligand 2,2′-Bi-1,10-phenanthroline and Its Remarkable Affinity for Cadmium(II)
  作者：Lyndsay E. Tucker、Galen C. Littman、Stuart Uritis、Joseph W. Nugent、Randolph P. Thummel、Joseph H. Reibenspies、S. Bart Jones、Hee-Seung Lee、Robert D. Hancock

  DOI：10.1021/acs.inorgchem.0c00361

  日期：2020.9.21

  fluorescence (CHEF) effect in BIPHEN complexes is discussed. The CHEF effect in the ZnII complex is somewhat smaller than that for CdII, which is discussed in terms of decreased overlap in the Zn–N bonds formed by the too small ZnII, leading to a partial photoinduced-electron-transfer quenching of fluorescence. The structure of the complex [Cd(BIPHEN)2](ClO4)2 is reported and shows that the Cd–N bonds

  据报道，对于多种金属离子，四齿配体2,2'-bi-1,10-菲咯啉（BIPHEN）在50％CH 3 OH / H 2 O中的金属离子络合特性。将BIPHEN（在主链上具有两个增强的苯并基）与其他四吡啶基，2,9-二（吡啶-2-基）-1,10-菲咯啉（DPP；具有一个苯并基）和2,2'：6进行比较′，2″：6″，2′-四吡啶（QPY；无苯甲酰基），其预组织水平为BIPHEN> DPP> QPY。通过跟踪存在金属离子时BIPHEN的吸收光谱中强烈的π→π*跃迁随pH的变化来确定形成常数。日志K 1值表明，与较少组织的四吡啶DPP和QPY相比，由两个苯并基产生的增加的预组织水平增加了BIPHEN配体的骨架，从而增强了大金属离子（离子半径大于0.9Å）的复杂稳定性。 。特别是，大的Cd II离子[log K 1（BIPHEN）= 12.7]显示出比小Zn II离子[log K 1（BIPHEN）=
• 2,2‘;9‘,2‘ ‘-Ter[1,10]phenanthroline
  作者：Ruifa Zong、Randolph P. Thummel

  DOI：10.1021/ic050712w

  日期：2005.8.1

  The title molecule, 2,2';9',2"-ter[1,10]phenanthroline can be prepared from 2,9-dichloro-1,10-phenanthroline in three steps through the corresponding diacetyl intermediate. The ligand acts as a hexadentate with K+, while two molecules form a trinuclear, helical complex with Cu(I), which evidences pi-stacking interactions and Cu-Cu distances of 3.01-3.04 angstrom. Electrochemical analysis shows a strong interaction between the Cu(I) centers.
• HAGINIWA J.; HIGUCHI Y.; KAWASHIMA T.; GOTO T., YAKUGAKU DZASSI, YAKUGAKU ZASSNI, J. PHARM. SOS. JAR. <YKKZ-AJ>, 1975, 95+
  作者：HAGINIWA J.、 HIGUCHI Y.、 KAWASHIMA T.、 GOTO T.

  DOI：——

  日期：——
• Bi-1,10-phenanthrolines and Their Mononuclear Ru(II) Complexes
  作者：Yi-Zhen Hu、Qin Xiang、Randolph P. Thummel

  DOI：10.1021/ic011126f

  日期：2002.7.1

  A series of four biphen (phen = 1,10-phenanthroline) ligands, 2,2'-biphen (1), 3,3'-biphen (2), 2,2'-dimethylene-3,3'-biphen (3), and 2,3'-dimethylene-3,2'-biphen (4), is prepared by coupling and Friedlander methodology. The corresponding mononuclear Ru(II) complexes, [Ru(1-4)(Mebpy)(2)](2+) where Mebpy = 4,4'-dimethyl-2,2'-bipyridine, are prepared. These complexes show long wavelength electronic absorptions at 441-452 nm and emissions at 622-641 nm. Metal-based oxidations occur in the range 1.18-1.21 V, and ligand-based reductions, at -1.20 to -1.30 V. The addition of Zn2+, Cd2+, or Hg2+ ions results in a strong enhancement and red shift of the luminescence of complex Ru-3. Alkali and alkaline earth metal ions barely affect the luminescence of Ru-3 while transition metal ions such as Co2+, Cu2+, Ni2+, and Mn2+ lead to efficient quenching of the Ru-3 luminescence. The luminescence of Ru-2 and Ru-4 is quenched in the presence of Zn2+ because of a conformationally induced reduction in electronic communication between the two phen halves of the ligand. The addition of Zn2+ has only a slight effect on the luminescence of Ru-1 because of steric hindrance toward complexation.