Ru(phtpy)Cl₃ | 146164-70-7

• 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: Ru(phtpy)Cl₃
• 英文别名: Ru(4'-phenyl-2,2':6',2''-terpyridine)Cl₃；[Ru(4′-phenyl-2,2′:6′,2″-terpyridine)Cl₃]；Ru(2,6-di(pyridin-2-yl)-4-phenylpyridine)Cl₃；4-phenyl-2,6-dipyridin-2-ylpyridine;trichlororuthenium
• CAS: 146164-70-7
• 化学式: C₂₁H₁₅Cl₃N₃Ru
• 分子量: 516.799
• InChiKey: FMNGCIQASILWPL-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：

  异喹啉 、 Ru(phtpy)Cl₃ 在 N-乙基吗啉 作用下， 以 乙醇 为溶剂， 反应 16.0h， 生成
  参考文献：
  名称：

  芳香族TpyRu 2+（L）2 Cl衍生物作为水氧化催化剂（Tpy = 2,2'：6'，2”-叔吡啶，Ru =钌，L =吡啶或异喹啉）

  摘要：

  设计并合成了几种具有[TpyRu 2+（Py）2 Cl] +和[TpyRu 2+（Isoq）2 Cl] +结构的单核配合物。这些配合物的结构通过NMR和ESI-MS证实，所有催化剂的性质也通过光学和电化学表征。通过周转数（TONs）检查了水氧化实验，该数显示了所有催化剂的催化性能。相比之下，吡啶官能化的1a - 1d比异喹啉配位化合物2a - 2d具有更高的催化活性。。还观察到，在联吡啶上连接的多环芳族基团对催化活性的影响有限。在这些钌络合物中，Ph-TpyRu 2+（Py）2 Cl的最高TON值为897。

  DOI：

  10.1016/j.catcom.2018.12.021
• 作为产物：
  描述：

  4-乙酰吡啶 在 ammonium hydroxide 、 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 16.0h， 生成 Ru(phtpy)Cl₃
  参考文献：
  名称：

  A selenium-containing ruthenium complex as a cancer radiosensitizer, rational design and the important role of ROS-mediated signalling

  摘要：

  我们已经描述了含硒钌配合物的合理设计，以及它们作为癌症放射增敏剂的使用，通过调节ROS介导的途径。

  DOI：

  10.1039/c4cc07926d

文献信息

• Chemical and photochemical behavior of ruthenium nitrosyl complexes with terpyridine ligands in aqueous media
  作者：Pablo Labra-Vázquez、Mathilde Bocé、Marine Tassé、Sonia Mallet-Ladeira、Pascal G. Lacroix、Norberto Farfán、Isabelle Malfant

  DOI：10.1039/c9dt04832d

  日期：——

  Cl) complexes. Six X-ray crystal structures are presented for cis(Cl,Cl)-[thiophenyl-tpyRuCl2(NO)](PF6) (cis-3a), trans(Cl,Cl)-[thiophenyl-tpyRuCl2(NO)](PF6) (trans-3a), trans(NO,OH)-[phenyl-tpyRu(Cl)(OH)(NO)](PF6) (4a), trans(NO,OH)-[thiophenyl-tpyRu(Cl)(OH)(NO)](PF6) (4b), trans(NO,OEt)-[phenyl-tpyRu(Cl)(OEt)(NO)](PF6) (5a), and trans(NO,OH)-[phenyl-tpyRu(Cl)(OEt)(NO)](PF6) (5b) compounds. The different

  一组各种顺式（Cl，Cl）-[R-tpyRuCl2（NO）]（PF6）和反式（Cl，Cl）-[R-tpyRuCl2（NO）]（PF6）（R的合成和行为＝芴基，苯基，噻吩基； tpy ＝ 2，2′：6′，2′-叔吡啶）配合物。在任何情况下，无论起始顺式/反式（Cl，Cl）配合物的性质如何，一个氯代配体均被羟基配体取代，最终物质以单一的反式（NO，OH）异构体形式出现。提出了六种X射线晶体结构，分别是顺式（Cl，Cl）-[硫代苯基-tpyRuCl2（NO）]（PF6）（顺式3a），反式（Cl，Cl）-[硫代苯基-tpyRuCl2（NO）]（PF6） ）（反式3a），反式（NO，OH）-[苯基-tpyRu（Cl）（OH）（NO）]（PF6）（4a），反式（NO，OH）-[噻吩-tpyRu（Cl） OH）（NO）]（PF6）（4b），反式（NO，OEt）-[苯基-tpyRu（Cl）（OEt）（NO
• 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。
• Ruthenium bistridentate complexes with non-symmetrical hexahydro-pyrimidopyrimidine ligands: a structural and theoretical investigation of their optical and electrochemical properties
  作者：Baptiste Laramée-Milette、Garry S. Hanan

  DOI：10.1039/c6dt02408d

  日期：——

  structural effect on the optical properties, density functional theory (DFT) and time-dependent DFT calculations have been implemented to enlighten the experimental data and prove that exciton coupling is at the origin of the observed shift. The electronic properties have been investigated and, as corroborated by electrochemical data, the presence of the hpp ligand strongly affects the oxidation potential

  基于三个带有强电子给体基团1,3,4,6,7,8-hexahydro-2 H-嘧啶[1,2- α ]嘧啶（hpp）的非对称三齿配体合成了六种钌配合物，bpyG（bpyG = 2,2'-联吡啶-6-hpp），phenG（phenG = 2-hpp-1,10-菲咯啉）和QpyG（QpyG = 2-hpp-6-喹啉基吡啶基）。的FAC - /聚体的均配型物种的-conformation对光学特性，其中一个显着的影响FAC-异构体的吸收发生红移150 nm，从而在大约850 nm处达到近红外。由于对光学性质的有趣结构影响，已实施了密度泛函理论（DFT）和时变DFT计算，以启发实验数据并证明激子耦合是观察到的位移的起源。已经研究了电子性质，并且通过电化学数据证实，hpp配体的存在强烈影响钌金属离子的氧化电位，这使得可以容易地微调电子性质。还研究了所有化合物的发光特性（最大λ发射光谱= 781–817
• Near infra-red emission from a mer-Ru(ii) complex: consequences of strong σ-donation from a neutral, flexible ligand with dual binding modes
  作者：Amlan K. Pal、Nelsi Zaccheroni、Sebastiano Campagna、Garry S. Hanan

  DOI：10.1039/c3cc49880h

  日期：——

  A rare example of dual coordination modes by a novel tridentate ligand gives rise to unique fac-and mer-Ru(II/III) complexes. The mer-RuII-complex displays the farthest red-shift of a triplet metal-to-ligand charge transfer (3MLCT) emission with a tridentate ligand for a mononuclear complex. This observation is a consequence of large bite angle and strong σ-donation by the ligand, the combined effect of which helps to separate the energy of the 3MLCT and 3MC states.

  一个新型三齿配体的双配位模式的罕见例子产生了独特的fac-和mer-Ru(II/III)复合物。mer-RuII-复合物显示出单核复合物中使用三齿配体时三重态金属-配体电荷转移（3MLCT）发射的最大红移。这个观察结果是由于配体的大咬角和强σ-供体效应所致，二者的联合作用有助于分离3MLCT和3MC状态的能量。
• Labile ruthenium(<scp>ii</scp>) complexes with extended phenyl-substituted terpyridyl ligands: synthesis, aquation and anticancer evaluation
  作者：Huaiyi Huang、Pingyu Zhang、Yu Chen、Liangnian Ji、Hui Chao

  DOI：10.1039/c5dt02446c

  日期：——

  The present study demonstrated that the anticancer activities of labile Ru(ii) complexes can be efficiently tuned by chelating with different phenyl-substituted terpyridyl ligands.

  本研究表明，通过与不同苯基取代的三吡啶配体螯合，可以有效调控易失性Ru(II)配合物的抗癌活性。