Ru(BrPh-dpt)Cl₃ | 879495-64-4

• 英文名称: Ru(BrPh-dpt)Cl₃
• CAS: 879495-64-4
• 化学式: C₁₉H₁₂BrCl₃N₅Ru
• 分子量: 597.671
• InChiKey: PMRDLBFROGSUNC-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  六氟磷酸钾 、 4′,4′′′′-(1,4-亚苯基)二(2,2′:6′,2′′-三联吡啶) 、 Ru(BrPh-dpt)Cl₃ 以 N,N-二甲基甲酰胺 为溶剂， 以50%的产率得到[(2,4-bis(2-pyridyl)-6-p-bromophenyl-1,3,5-triazine)Ru(1,4-bis(2,2':6',2''-terpyridin-4'-yl)benzene)Ru(2,4-bis(2-pyridyl)-6-p-bromophenyl-1,3,5-triazine)](PF6)4*KPF6
  参考文献：
  名称：

  含双吡啶-1,3,5-三嗪配体的棒状双核Ru（II）络合物中的光诱导能量转移

  摘要：

  制备并表征了三种新的棒状双核Ru（II）多吡啶化合物，并对其进行了表征吸收光谱通过常规的稳态吸收和发光光谱方法以及在纳秒和飞秒时间范围内运行的时间分辨方法，已经研究了氧化还原行为和光物理性质。所有的新物种都包含1,4-双（2,2'：6'，2''-三联吡啶-4'-基）苯（4）配体和2,4-双（2-吡啶基）-6-对-溴苯基-1,3,5-三嗪和/或4'-（对-溴苯基）-2,2'：6'，2''-吡啶外围设备配体。特别是1和2是对称二元组，因为Ru（II）离子带有相同的外围配体 （这 三嗪-基于 配体在1和特吡啶-基于 配体在2的情况下，而3是不对称的二元组，因为它的两个Ru（II）中心带有两个不同的外围配体 （有关化合物的结构式，请参见 图1）。这吸收光谱新化合物的氧化还原行为表明二元组的每个亚基在双核系统中均保持其独特的特性，这是确认系统超分子性质的必要条件。所有物种都表现出金属到金属配体 电荷

  DOI：

  10.1039/b820444f
• 作为产物：
  描述：

  水合三氯化钌 、 2,4-di(2'-pyridyl)-6-(p-bromo-phenyl)-1,3,5-triazine 以 乙醇 为溶剂， 生成 Ru(BrPh-dpt)Cl₃
  参考文献：
  名称：

  Paramagnetic Ru(III) complexes of tridentate ligands: Characterization of useful intermediates for heteroleptic Ru(II) complexes

  摘要：

  Paramagnetic Cl3Ru(L) complexes of tridentate ligands (2a: L = 1a = 4'-(p-bromophenyl)-2,2':6',2 ''-terpyridine; 2b: L = 1b = 6-(p-bromophenyl)-2,4-dipyrid-2-yl-1,3,5-triazine) were synthesized in a high-yield method with facile isolation of these useful synthons. The complexes were isolated in high purity and were characterized by several methods, including standard techniques such as H-1 NMR and electrospray ionization mass spectrometry. The H-1 NMR of the complexes displayed peaks from +10 to 37 ppm, with the protons ortho to the nitrogen atoms coordinated to the paramagnetic centre being shifted the most (2a: H-6.6 '' = -35.3 ppm; 2b: H-6.6 '' = -26.1 ppm), while the protons on the non-bonding phenyl rings were relatively unchanged with respect to their uncomplexed ligands. The electronic absorption spectra of the complexes displayed both (LMCT)-L-1 bands (Cl-to-Ru, 2a: lambda max= 405 nm; 2b: lambda max = 420 nm) and (MLCT)-M-1 (Ru-to-L, 2a: lambda max = 486 nm; 2b: lambda max = 567 nm) bands. Due to the ease of purification and high yields, the use of complex 3, first introduced by Chatt, is the method of choice to form Cl3Ru(L) complexes of tridentate ligands. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.inoche.2010.12.011

文献信息

• Near infra-red emitting Ru(<scp>ii</scp>) complexes of tridentate ligands: electrochemical and photophysical consequences of a strong donor ligand with large bite angles
  作者：Amlan K. Pal、Scolastica Serroni、Nelsi Zaccheroni、Sebastiano Campagna、Garry S. Hanan

  DOI：10.1039/c4sc01604a

  日期：——

  A novel N^N^N tridentate ligand dgpy (dgpy = 2,6-diguanidylpyridine) was synthesized by a Pd-catalyzed C–N bond-forming reaction. A novel family of [RuII(tpy')(dgpy)](PF6)2 (1 and 2) or [RuII(dpt')(dgpy)](PF6)2 (3 and 4) (tpy' = substituted-2,2′:6′,2′-terpyridine, dpt' = substituted-2,4-dipyrid-2′-yl-1,3,5-triazine) complexes are reported. The dgpy ligand (80%) and the heteroleptic complexes 1–4 (37–60%) were obtained in modest to good yields. The dgpy ligand and its complexes were fully characterized by a variety of techniques including X-ray crystallography and density functional theory (DFT). In cyclic voltammetric studies, the complexes exhibit a RuIII/II couple, which is 600–800 mV less positive than the RuIII/II couple in [Ru(tpy)2]2+. The 1MLCT absorption maxima of all the complexes (620–740 nm) are considerably red-shifted as compared to that of [Ru(tpy)2]2+ (474 nm). The 3MLCT emission maxima of complexes 1 and 2 are also red-shifted by about 270 nm compared to that of [Ru(tpy)2]2+ (629 nm) at room temperature (298 K), whereas the corresponding maxima for complexes 3 and 4 are shifted by about 330 nm at 77 K. The relative trends in redox potentials and 1MLCT maxima are in good agreement with DFT and TD-DFT calculations. Complexes 1 and 2 emit from a RuII-to-tpy 3MLCT state, which is rarely the emitting state at λ > 850 nm in [Ru(tpy)(N^N^N)]2+ complexes when the ancillary ligand is neutral. Complexes 1 and 2 also exhibit long excited-state lifetimes (τ ∼ 100 ns) at room temperature with associated quantum yield (Φ) of 0.001. The reported τ and Φ values are approximately 400–500 times and 1000 times higher compared to those of [Ru(tpy)2]2+ (τ = 0.25 ns, Φ ≤ 5 × 10−6), respectively. Complexes 3 and 4 emit from a RuII-to-dpt 3MLCT state, albeit only at 77 K (τ = 0.25 ns) due to rapid deactivation of their 3MLCT state according to the energy-gap law. The improved photophysical properties of the complexes are consequences of enlarged separation of the 3MLCT–3MC states, due to the strong donation and larger bite angles of the dgpy ligand.

  一种新型的N^N^N三齿配体dgpy（dgpy = 2,6-二氨基吡啶）通过Pd催化的C–N键形成反应合成。报道了一类新型的[RuII(tpy')(dgpy)](PF6)2（1和2）或[RuII(dpt')(dgpy)](PF6)2（3和4）（tpy' = 替代-2,2′:6′,2′-萜吡啶，dpt' = 替代-2,4-二吡啶-2′-基-1,3,5-三嗪）复合物。dgpy配体（80%）和异配体复合物1–4（37–60%）的产率中等到良好。利用多种技术对dgpy配体及其复合物进行了全面表征，包括X射线晶体学和密度泛函理论（DFT）。在循环伏安研究中，这些复合物展示了RuIII/II对，电位比[Ru(tpy)2]2+中的RuIII/II对降低了600–800毫伏。所有复合物的1MLCT吸收最大值（620–740 nm）相较于[Ru(tpy)2]2+（474 nm）显著红移。复合物1和2的3MLCT发射最大值在室温（298 K）下也相比[Ru(tpy)2]2+（629 nm）红移了约270 nm，而复合物3和4在77 K下的对应最大值则红移约330 nm。氧化还原电位和1MLCT最大值的相对趋势与DFT和TD-DFT计算结果较为一致。复合物1和2从RuII到tpy的3MLCT态发射，这在伴随配体为中性时的[Ru(tpy)(N^N^N)]2+复合物中较为少见，且λ > 850 nm时发射状态的出现较为罕见。复合物1和2在室温下呈现长的激发态寿命（τ ∼ 100 ns），伴随的量子产率（Φ）为0.001。报告的τ和Φ值分别约比[Ru(tpy)2]2+（τ = 0.25 ns，Φ ≤ 5 × 10−6）高出400–500倍和1000倍。复合物3和4仅在77 K下从RuII到dpt的3MLCT态发射（τ = 0.25 ns），这是因为根据能隙法，它们的3MLCT态迅速非辐射性去活化。复合物的光物理特性改善是由于dgpy配体的强供体效应和更大的咬合角导致3MLCT–3MC态的分离增大。
• Long-lived, red-emitting excited state of a Ru(II) complex of a diaminotriazine ligand
  作者：Amlan K. Pal、Adam Duong、James D. Wuest、Garry S. Hanan

  DOI：10.1016/j.poly.2015.11.009

  日期：2016.3

  Heteroleptic complexes of Ru(II) with tridentate ligand Py-DAT2 (2,6-bis(4,6-diamino-1,3,5-triazin-2-yl)pyridine) and with derivatives of tridentate ligands tpy (2,2′:6′,2″-terpyridine) or dpt (2,6-dipyridyltriazine) have been synthesized and characterized. Changing the second ligand from tpy to dpt was found to profoundly alter the electronic and photophysical properties of the complexes. Structural

  摘要Ru（II）与三齿配体Py-DAT2（2,6-双（4,6-二氨基-1,3,5-三嗪-2-基）吡啶）以及三齿配体tpy（2合成并表征了，2'：6'，2''-吡啶）或dpt（2,6-二吡啶基三嗪）。发现将第二种配体从tpy改变为dpt可以深刻改变复合物的电子和光物理性质。通过单晶XRD对Py-DAT2 / tpy络合物进行结构分析，发现存在2D叔吡啶基环抱和氢键的扩展阵列，其中涉及结晶水和Py-DAT2的氨基。
• Dinuclear Ru(ii) complexes of bis-(dipyrid-2′-yl)triazine (bis-dpt) ligands as efficient electron reservoirs
  作者：Marie-Pierre Santoni、Garry S. Hanan、Bernold Hasenknopf、Anna Proust、Francesco Nastasi、Scolastica Serroni、Sebastiano Campagna

  DOI：10.1039/c0cc03245j

  日期：——

  A planar bis-dipyrid-2′-yltriazine (bis-dpt) bridging ligand forms dinuclear Ru(II) complexes able to store up to eight electrons upon electrochemical reduction.

  平面双二吡啶-2²-四嗪（双二吡啶）桥联配体形成二核Ru（II）配合物，在电化学还原时能够储存多达八个电子。