bis(5,5'-dimethyl-2,2'-bipyridin-6-yl)ethyne | 146548-28-9

• 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: bis(5,5'-dimethyl-2,2'-bipyridin-6-yl)ethyne
• 英文别名: 3-methyl-2-[2-[3-methyl-6-(5-methylpyridin-2-yl)pyridin-2-yl]ethynyl]-6-(5-methylpyridin-2-yl)pyridine
• CAS: 146548-28-9
• 化学式: C₂₆H₂₂N₄
• 分子量: 390.487
• InChiKey: RIHLGTRNQCYWRX-UHFFFAOYSA-N

物化性质

• 熔点：
  214-215 °C
• 沸点：
  620.8±55.0 °C(predicted)
• 密度：
  1.22±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.23
• 重原子数：
  30.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  51.56
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  锇二(2,2'-联吡啶)氯化物 、 bis(5,5'-dimethyl-2,2'-bipyridin-6-yl)ethyne 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  Triplet Energy Transfer within Closely Spaced Positional Isomers of Ru/Os Polypyridine-Based Heterodiads

  摘要：

  A series of ditopic ligands has been synthesized in which terminal 2,2'-bipyridyl (bpy) groups are connected via an ethynylene group through different sites on the pyridine ring. These terminals have been capped with [Ru(bpy)(2)](2+) and [Os(bpy)(2)](2+) metallo-fragments to form photoactive heterodiads. In each case, quantitative intramolecular triplet energy transfer takes place along the molecular axis from the Ru-based terminal to its Os-based counterpart. Energy transfer, which is believed to involve through-bond electron exchange, is extremely fast and only slightly dependent on the geometry of the bridging ditopic ligand. Evaluation of vibronic overlap integrals, using Dexter-type formulism, or factors for the Franck-Condon weighted density of states, using Meyer's approach, allows estimation of the matrix elements for electron exchange. The two methods give comparable results, and it appears that electronic coupling within the triplet manifold is both modest and insensitive to the site at which the bridge is connected to the metal complexes. There exists a shallow relationship between the rate of electron exchange and the energy gap between triplets localized on donor and bridge, suggesting that this latter species participates in the energy-transfer process as a virtual state. Triplet energy transfer can also be considered in terms of a simultaneous two-electron, two-site exchange involving both LUMOs and HOMOs of the bridging ligand, with electron transfer through the LUMO being promoted by selective charge injection into the ditopic ligand under illumination. In this case, the products of the atomic orbital coefficients that describe coupling into and out of the bridge at the tripler level control the rate of energy transfer.

  DOI：

  10.1021/jp9842805
• 作为产物：
  描述：

  6-<2-(trimethylsilyl)-1-ethynyl>-5,5'-dimethyl-2,2'-bipyridine 在 四(三苯基膦)钯 potassium fluoride 、 二异丙胺 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 bis(5,5'-dimethyl-2,2'-bipyridin-6-yl)ethyne
  参考文献：
  名称：

  新型共价连接的双核钌（II）和三核钌（II）-铜（I）联吡啶配合物的合成，表征和性质

  摘要：

  合成了带有两个联吡啶亚基和乙炔基或二乙炔基桥的新的对位配体，并显示出它们形成了一系列新型的阳离子单核钌（II）和铜（I），双核钌（II）和三核钌（II）-铜（我）复杂。

  DOI：

  10.1039/dt9930000817

文献信息

• Synthesis and properties of novel ditopic polypyridine ligands bridged by one and two acetylenic bonds
  作者：Vincent Grosshenny、Raymond Ziessel

  DOI：10.1016/s0040-4039(00)74721-6

  日期：1992.12

  bipyridine or terpyridine subunits, in the presence of catalytic amounts of Pdo(PPh3)4 to yield, the new homo- and heteroditopic ethynyl bridge ligands 2a, 4a, 7a and 8. Self coupling of the ethynyl substituted bipyridine species in the presence of CuCl/TMEDA/O2, yield the symmetric diethynyl bridge ligands 2b, 4b and 7b.

  乙炔基取代的联吡啶螯合物与溴或三氟甲磺酸酯官能化联吡啶或三联吡啶亚基在催化量的Pd o（PPh 3）4存在下反应，生成新的均位和异位乙炔基桥配体2a，4a，7a和8。在CuCl / TMEDA / O 2存在下乙炔基取代联吡啶的自偶联产生对称的二乙炔基桥配体2b，4b和7b。
• 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.