4-(p-bromophenyl)-6-(m-tolyl)-2,2'-bipyridine | 1008133-62-7

• 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: 4-(p-bromophenyl)-6-(m-tolyl)-2,2'-bipyridine
• 英文别名: 4-(p-bromophenyl)-6-(m-tolyl)bipyridine；mtbpyH-Φ-Br；mtbpyH-.vphi.-Br；4-(4-Bromophenyl)-2-(3-methylphenyl)-6-pyridin-2-ylpyridine；4-(4-bromophenyl)-2-(3-methylphenyl)-6-pyridin-2-ylpyridine
• CAS: 1008133-62-7
• 化学式: C₂₃H₁₇BrN₂
• 分子量: 401.305
• InChiKey: BFVUIOQIBYRZTM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(p-bromophenyl)-6-(m-tolyl)-2,2'-bipyridine 、 联硼酸新戊二醇酯 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride potassium acetate 作用下， 以 二甲基亚砜 为溶剂， 生成 mtbpyH-Φ-B
  参考文献：
  名称：

  Cyclometallated, bis-terdentate iridium complexes as linearly expandable cores for the construction of multimetallic assemblies

  摘要：

  由两个三齿环金属配位体组成的环金属化铱配合物，其形式为[Ir(N⁁C⁁N)(N⁁N⁁C)]+，已被探索用于通过钯催化的交叉偶联反应制备多金属体系。我们制备了一种带有硼酸酯基的 N⁁N⁁C 配位配体，并将其与铱络合，得到了这种类型的硼酸附加络合物 3。这种络合物与溴代双三吡啶铱络合物发生交叉耦合，得到了双核铱化合物 6，其中两个铱中心之一是 N6 配位，另一个是 N4C2 配位。同时，溴代配合物 4 与硼酸添加的钌配合物偶联，得到双核异金属配合物 8，该配合物可通过原位溴化激活第二次偶联，从而获得线性 Ir-Ir-Ru 三金属组合物 11。我们对这些体系的电化学和发光特性进行了研究。就 8 和 11 而言，其行为可以用超分子描述来合理解释：从 Ir 末端到 Ru 发生了有效的能量转移。相反，对于化合物 6 来说，具有显著桥特性的激发态似乎在决定发射特性方面起着关键作用。

  DOI：

  10.1039/b821161b

文献信息

• A New Class of Iridium Complexes Suitable for Stepwise Incorporation into Linear Assemblies: Synthesis, Electrochemistry, and Luminescence
  作者：Victoria L. Whittle、J. A. Gareth Williams

  DOI：10.1021/ic701788d

  日期：2008.8.4

  A new family of cationic iridium(III) complexes is reported that contain two cyclometalating terdentate ligands. The complex [Ir(NCN-dpyx)(NNC-phbpy)](+) (1) contains one NCN-coordinating ligand, cyclometalating through the central phenyl ring, and one NNC-coordinated ligand, cyclometalated at the peripheral phenyl ring [dpyxH = 1,3-di(2-pyridyl)-4,6-dimethylbenzene; phbpyH = 6-phenyl-2,2'-bipyridine]. This binding mode dictates a mutually cis arrangement of the cyclometalated carbon atoms: the complexes are thus bis-terdentate analogues of the well-known [Ir(NC-ppy)(2)(NN-bpy)](+) family of complexes, which similarly contain acis-C2N4 coordination environment. The dpyx ligand can be brominated regioselectively at the carbon atom para to the metal under mild conditions. Starting from a modified complex, [Ir(NCN-dpyx)(NNC-mtbpy-phi-Br)](+) (2), which incorporates a pendent bromophenyl group, a sequential cross-coupling-bromination-cross-coupling strategy can be applied for the stepwise introduction of aryl groups into the ligands, using in situ palladium-catalyzed Suzuki reactions with arylboronic acids [mtbpyH-phi-Br = 4-(p-bromophenyl)-6-(m-tolyl)bipyridine]. Dimetallic complexes 6 and 7 have similarly been prepared by a palladium-catalyzed reaction of complex 2 with 1,4-benzenediboronic acid and 4,4'-biphenyldiboronic acid, respectively. All five monometallic complexes and both dimetallic systems are luminescent in solution, emitting around 630 nm in MeCN at 298 K, with quantum yields in the range of 0.02-0.06, superior to [Ir(ppy)(2)(bpy)](+). The luminescence, electrochemistry, and singlet-oxygen-sensitizing abilities of the new family of complexes are discussed in the context of the tris-bidentate analogues and related bis-terdentate compounds that contain a trans arrangement of cyclometalated carbon atoms.
• Cyclometallated, bis-terdentate iridium complexes as linearly expandable cores for the construction of multimetallic assemblies
  作者：Victoria L. Whittle、J. A. Gareth Williams

  DOI：10.1039/b821161b

  日期：——

  Cyclometallated iridium complexes comprised of two terdentate cyclometallating ligands, of the form [Ir(N⁁C⁁N)(N⁁N⁁C)]+, have been explored for the preparation of multimetallic systems by palladium-catalysed cross-coupling reactions. An N⁁N⁁C-coordinating ligand carrying a boronate ester group has been prepared and complexed to iridium to give a boronic acid appended complex of this type, 3. This complex has been subjected to cross-coupling with a bromo-substituted bis-terpyridyl iridium complex to give a dinuclear iridium compound 6, in which one of the two iridium centres is N6-coordinated and the other has an N4C2-coordination sphere. Meanwhile, a bromo-substituted complex 4 has been coupled with a boronic acid-appended ruthenium complex, to give a dinuclear heterometallic complex 8 that can be activated to a second coupling by in situ bromination, offering access to a linear Ir–Ir–Ru trimetallic assembly 11. The electrochemical and luminescence properties of these systems are investigated. In the case of 8 and 11, the behaviour can be rationalised in terms of a supramolecular description: efficient energy transfer occurs from the Ir terminus to the Ru. In contrast, for compound 6, an excited state with significant bridge character appears to play a key role in determining the emission properties.

  由两个三齿环金属配位体组成的环金属化铱配合物，其形式为[Ir(N⁁C⁁N)(N⁁N⁁C)]+，已被探索用于通过钯催化的交叉偶联反应制备多金属体系。我们制备了一种带有硼酸酯基的 N⁁N⁁C 配位配体，并将其与铱络合，得到了这种类型的硼酸附加络合物 3。这种络合物与溴代双三吡啶铱络合物发生交叉耦合，得到了双核铱化合物 6，其中两个铱中心之一是 N6 配位，另一个是 N4C2 配位。同时，溴代配合物 4 与硼酸添加的钌配合物偶联，得到双核异金属配合物 8，该配合物可通过原位溴化激活第二次偶联，从而获得线性 Ir-Ir-Ru 三金属组合物 11。我们对这些体系的电化学和发光特性进行了研究。就 8 和 11 而言，其行为可以用超分子描述来合理解释：从 Ir 末端到 Ru 发生了有效的能量转移。相反，对于化合物 6 来说，具有显著桥特性的激发态似乎在决定发射特性方面起着关键作用。