1,4-bis(2,2'-bipyridine-5-ethynyl) | 187026-94-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1,4-bis(2,2'-bipyridine-5-ethynyl)
• 英文别名: bis(2,2'-bipyridin-5-yl)butadiyne；bpyCCCCbpy；Bis(2,2-bipyridin-5-yl)butadiyne；2-pyridin-2-yl-5-[4-(6-pyridin-2-ylpyridin-3-yl)buta-1,3-diynyl]pyridine
• CAS: 187026-94-4
• 化学式: C₂₄H₁₄N₄
• 分子量: 358.402
• InChiKey: YGJXNFQUDXCDDQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• 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：

  dichlorobis(dimethyl sulfoxide)platinum(II) 、 1,4-bis(2,2'-bipyridine-5-ethynyl) 以 乙腈 为溶剂， 以78%的产率得到Pt(bis(2,2-bipyridin-5-yl)butadiyne)Cl2
  参考文献：
  名称：

  Sensitization of lanthanide luminescence by two different Pt → Ln energy transfer pathways in PtLn3 heterotetranuclear complexes with 5-ethynyl-2,2′-bipyridine

  摘要：

  5-[2-(trimethylsill)-1-ethynyl]-2,2â²-bipyridine (Me3SiCCbpy) 与 Pt(bpy)Cl2 (bpy = 2,2â²-bipyridine) 和 Pt(bpyCCâCCbpy)Cl2 (bpyCCâCCbpy = bis(2. 2â²-bipyridin-5-yl)butadiyne) 的反应诱导分离出 Pt(bpy)(CCbpy)2 (1) 和 Pt(bpyCCâCCbpy) (2)、2,2â²-联吡啶-5-基）丁二炔）分别诱导分离出 Pt(bpy)(CCbpy)2 (1) 和 Pt(bpyCCâCCbpy)(CCbpy)2 (5)。将 Ln(hfac)3(H2O)2（hfac = 六氟乙酰丙酮）与 1 或 5 结合，可得到相应的 PtLn2（Ln = Nd (2)、Eu (3)、Yb (4)）或 PtLn3 阵列（Ln = Nd (6)、Eu (7)、Gd (8)、Yb (9)）。铂（2,2â²-联吡啶）（乙酰基）2发色团的MLCT吸收区为360⤠Π"ex⤠480纳米，在此激发下，通过从PtII天线发色团进行高效的PtâLn能量转移，成功实现了敏化镧系元素发光。与PtâCCbpyâLn（Ptâ¯Ln = 8.6 Ã）阵列中相当高效的PtâLn能量转移相比，PtâbpyCCâCCbpyâLn（Ptâ¯Ln = 13.3 Ã）阵列中的能量转移效率较低，原因是后者的Ptâ¯Ln间距更长。

  DOI：

  10.1039/b801573b
• 作为产物：
  描述：

  5-溴-2,2’-联吡啶 在 bis-triphenylphosphine-palladium(II) chloride 、 potassium fluoride 、 copper(l) iodide 、 氧气 、 二异丙胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 为溶剂， 生成 1,4-bis(2,2'-bipyridine-5-ethynyl)
  参考文献：
  名称：

  Construction of Preorganized Polytopic Ligands via Palladium-Promoted Cross-Coupling Reactions

  摘要：

  Rigid preorganized multitopic ligands have been designed and synthesized. The Pd(O)-catalyzed cross-coupling reactions between ethynylated derivatives of bipyridine or terpyridine and the corresponding bipyridine or terpyridine halides or triflates provide access to various homo-ditopic, hetero-ditopic, homo-tritopic, and hetero-tritopic ligands bearing acetylene or diphenylacetylene central units in fair to excellent yields. Optimal conditions mere found with [Pd(PPh(3))(2)Cl-2], CuI in THF and diisopropylamine at rt, or with [Pd(PPh(3))(4)] in benzene and diisopropylamine at 80 degrees C. When a phenylethynyl group is present in the molecule, the relevant conditions involve [Pd(PPh(3))(4)] in n-propylamine at 60 degrees C. Oxidative dimerization of the ethynylated derivatives in the presence of cupric salts and oxygen gives the corresponding homo-ditopic ligands bearing diacetylene or diphenyldiacetylene as a spacer in good yields. These methods provide a practical approach to the rational design of multichelating ligands for coordination of redox and photoactive transition metals.

  DOI：

  10.1021/jo962068w

文献信息

• Syntheses, characterization and redox properties of oxo-centred triruthenium cluster dimers and trimers linked by ortho-metallated polypyridyl ligands
  作者：Feng-Rong Dai、Jing-Lin Chen、Heng-Yun Ye、Li-Yi Zhang、Zhong-Ning Chen

  DOI：10.1039/b717315f

  日期：——

  m-dash]Cbpy), 2,2'-bipyrazine (bpz), pyrazino[2,3-f]quinoxaline (pyq), or 4,7-phenanthroline (4,7-phen). As revealed by redox wave splitting, electronic interactions are operating between two Ru3O redox centres in most of the triruthenium cluster dimers and trimers. The cluster-cluster interactions are highly sensitive to the variations in bonding modes of the polypyridyl ligands. Ortho-metallation

  通过以氧为中心的三钌前体化合物[Ru3O（OAc）6（py）2（CH3OH）] +（1 ）与双（2,2'-联吡啶-5-基）丁二炔（bpyC [三键，长度为m-破折号] CC [三键，长度为m-破折号Cbpy），bis（2,2'-双pridin -5-基）乙炔（bpyC [三键，长度为m-破折号Cbpy），2,2'-联吡嗪（bpz），吡嗪并[2,3-f]喹喔啉（pyq）或4,7-菲咯啉（4,7-phen）。正如氧化还原波分裂所揭示的，大多数三钌簇二聚体和三聚体中的两个Ru3O氧化还原中心之间存在电子相互作用。簇-簇相互作用对聚吡啶基配体的键合模式的变化高度敏感。
• Electron Delocalization in Ruthenium(II) and Osmium(II) 2,2‘-Bipyridyl Complexes Formed from Ethynyl-Bridged Ditopic Ligands
  作者：Vincent Grosshenny、Anthony Harriman、Francisco M. Romero、Raymond Ziessel

  DOI：10.1021/jp9616268

  日期：1996.1.1

  series of mono- and binuclear ruthenium(II) and osmium(II) 2,2‘-bipyridyl complexes that contain an ethynyl-bridged ditopic ligand. In particular, the electrochemical properties are indicative of electron delocalization over an extended π*-orbital in the π-radical anions. The site of attachment of the ethynyl substituent to the 2,2‘-bipyridyl ring affects the various properties, especially absorption and

  已记录了一系列含有乙炔基桥接的对位配体的单核和双核钌（II）和（II）2,2'-联吡啶配合物的光物理和电化学性质。特别地，电化学性质指示在π自由基阴离子中的扩展π*轨道上的电子离域。乙炔基取代基与2,2'-联吡啶基环的连接位置会影响各种性质，尤其是吸收和发射光谱的最大值。在大多数情况下，最低能量三重态激发态的非辐射失活速率比没有共轭取代基的相应配合物的预期慢。就电子在三重态内的部分对位配体上的电子离域作用而言，该效应是合理的，并且其重要性显着取决于所讨论的络合物的三重态能量。最低能量的三重态在某种程度上与更牢固地耦合到基态的上层三重态混合。根据金属络合物的性质，这种较高能的三重态可能来自（i）从金属中心到母体配体的电荷转移；（ii）位于对位配体上的π，π*状态，或（iii）金属中心的激发态。对于Os 这种较高能量的三重态可能源自（i）从金属中心到母体配体的电荷转移；（ii）局部位于对位配体
• Construction of Preorganized Polytopic Ligands via Palladium-Promoted Cross-Coupling Reactions
  作者：Vincent Grosshenny、Francisco M. Romero、Raymond Ziessel

  DOI：10.1021/jo962068w

  日期：1997.3.1

  Rigid preorganized multitopic ligands have been designed and synthesized. The Pd(O)-catalyzed cross-coupling reactions between ethynylated derivatives of bipyridine or terpyridine and the corresponding bipyridine or terpyridine halides or triflates provide access to various homo-ditopic, hetero-ditopic, homo-tritopic, and hetero-tritopic ligands bearing acetylene or diphenylacetylene central units in fair to excellent yields. Optimal conditions mere found with [Pd(PPh(3))(2)Cl-2], CuI in THF and diisopropylamine at rt, or with [Pd(PPh(3))(4)] in benzene and diisopropylamine at 80 degrees C. When a phenylethynyl group is present in the molecule, the relevant conditions involve [Pd(PPh(3))(4)] in n-propylamine at 60 degrees C. Oxidative dimerization of the ethynylated derivatives in the presence of cupric salts and oxygen gives the corresponding homo-ditopic ligands bearing diacetylene or diphenyldiacetylene as a spacer in good yields. These methods provide a practical approach to the rational design of multichelating ligands for coordination of redox and photoactive transition metals.
• Sensitization of lanthanide luminescence by two different Pt → Ln energy transfer pathways in PtLn3 heterotetranuclear complexes with 5-ethynyl-2,2′-bipyridine
  作者：Hai-Bing Xu、Li-Yi Zhang、Zhong-Hui Chen、Lin-Xi Shi、Zhong-Ning Chen

  DOI：10.1039/b801573b

  日期：——

  Reactions of 5-[2-(trimethylsilyl)-1-ethynyl]-2,2′-bipyridine (Me3SiCCbpy) with Pt(bpy)Cl2 (bpy = 2,2′-bipyridine) and Pt(bpyCC–CCbpy)Cl2 (bpyCC–CCbpy = bis(2,2′-bipyridin-5-yl)butadiyne) induced isolation of Pt(bpy)(CCbpy)2 (1) and Pt(bpyCC–CCbpy)(CCbpy)2 (5), respectively. Incorporating Ln(hfac)3(H2O)2 (hfac = hexafluoroacetylacetone) with 1 or 5 gave the corresponding PtLn2 (Ln = Nd (2), Eu (3), Yb (4)) or PtLn3 arrays (Ln = Nd (6), Eu (7), Gd (8), Yb (9)). With excitation at 360 ≤ λex ≤ 480 nm, which is the MLCT absorption region of the Pt(2,2′-bipyridyl)(acetylide)2 chromophore, sensitized lanthanide luminescence is successfully attained by efficient Pt → Ln energy transfer from the PtII antenna chromophores. In contrast with quite efficient Pt → Ln energy transfer in the Pt–CCbpy–Ln (Pt⋯Ln = 8.6 Å) array, energy transfer transmitted across the Pt–bpyCC–CCbpy–Ln (Pt⋯Ln = 13.3 Å) array is less efficient owing to the much longer Pt⋯Ln separation in the latter.

  5-[2-(trimethylsill)-1-ethynyl]-2,2â²-bipyridine (Me3SiCCbpy) 与 Pt(bpy)Cl2 (bpy = 2,2â²-bipyridine) 和 Pt(bpyCCâCCbpy)Cl2 (bpyCCâCCbpy = bis(2. 2â²-bipyridin-5-yl)butadiyne) 的反应诱导分离出 Pt(bpy)(CCbpy)2 (1) 和 Pt(bpyCCâCCbpy) (2)、2,2â²-联吡啶-5-基）丁二炔）分别诱导分离出 Pt(bpy)(CCbpy)2 (1) 和 Pt(bpyCCâCCbpy)(CCbpy)2 (5)。将 Ln(hfac)3(H2O)2（hfac = 六氟乙酰丙酮）与 1 或 5 结合，可得到相应的 PtLn2（Ln = Nd (2)、Eu (3)、Yb (4)）或 PtLn3 阵列（Ln = Nd (6)、Eu (7)、Gd (8)、Yb (9)）。铂（2,2â²-联吡啶）（乙酰基）2发色团的MLCT吸收区为360⤠Π"ex⤠480纳米，在此激发下，通过从PtII天线发色团进行高效的PtâLn能量转移，成功实现了敏化镧系元素发光。与PtâCCbpyâLn（Ptâ¯Ln = 8.6 Ã）阵列中相当高效的PtâLn能量转移相比，PtâbpyCCâCCbpyâLn（Ptâ¯Ln = 13.3 Ã）阵列中的能量转移效率较低，原因是后者的Ptâ¯Ln间距更长。