(4′-hydroxy-2,2′:6′,2″-terpyridyl)(trichloro)ruthenium(III) | 146164-66-1

• 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′-hydroxy-2,2′:6′,2″-terpyridyl)(trichloro)ruthenium(III)
• 英文别名: RuCl₃(4′-hydroxy-2,2′:6′,2″-terpyridine)；Ru(2,2':6',2''-terpyridin-4'(1'H)-one)Cl3；(2,2':6',2''-terpyridin-4'-ol)ruthenium trichloride；{Ru(4'-OH-2,2':6',2''-terpyridine)Cl3}；[Ru(4'-hydroxy-2,2':6',2''-terpyridine)Cl3]；[Ru(HOtpy)Cl3]；2,6-dipyridin-2-yl-1H-pyridin-4-one;trichlororuthenium
• CAS: 146164-66-1
• 化学式: C₁₅H₁₁Cl₃N₃ORu
• 分子量: 456.701
• InChiKey: ANJYVQWSDJABQG-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：

  (4′-hydroxy-2,2′:6′,2″-terpyridyl)(trichloro)ruthenium(III) 在 三乙胺 作用下， 以 乙醇 为溶剂， 反应 2.0h， 生成 bis-((4′-hydroxy-2,2′:6′,2″-terpyridyl)(chloro)ruthenium) dichloride
  参考文献：
  名称：

  Immobilising molecular Ru complexes on a protective ultrathin oxide layer of p-Si electrodes towards photoelectrochemical CO₂ reduction

  摘要：

  钌配合物通过自然的SiOx层从照射的p型硅中提取电子，产生570 mV的光电压。

  DOI：

  10.1039/d1dt01331a
• 作为产物：
  描述：

  2,6-双(2-吡啶基)-4(1H)-吡啶酮 、 三氯化钌 以 乙醇 为溶剂， 生成 (4′-hydroxy-2,2′:6′,2″-terpyridyl)(trichloro)ruthenium(III)
  参考文献：
  名称：

  A new convergent strategy for high-nuclearity metallodendrimers

  摘要：

  描述了一种合成金属树枝状大分子的收敛性方法，其中关键步骤是含有配位亲核试剂的金属配合物与多功能亲电试剂的反应；利用这种方法，制备了线性和星型四、六和九钌金属树枝状大分子。

  DOI：

  10.1039/cc9960000033

文献信息

• Critical Hammett Electron-Donating Ability of Substituent Groups for Efficient Water Oxidation Catalysis by Mononuclear Ruthenium Aquo Complexes
  作者：Shunsuke Watabe、Yuki Tanahashi、Masanari Hirahara、Hirosato Yamazaki、Kosuke Takahashi、Eman A. Mohamed、Yuta Tsubonouchi、Zaki N. Zahran、Kenji Saito、Tatsuto Yui、Masayuki Yagi

  DOI：10.1021/acs.inorgchem.9b01623

  日期：2019.10.7

  [Ru(Rtpy)(bpy)(H2O)]2+ (1R; bpy = 2,2′-bipyridine, and Rtpy = 2,2′:6′,2″-terpyridine derivatives) complexes with a variety of 4′-substituent groups on Rtpy were synthesized and characterized to reveal the effects of substituents on their structures, physicochemical properties, and catalytic activities for water oxidation. The geometric structures of 1R are not considerably influenced by the electron-donating

  [Ru（Rtpy）（bpy）（H 2 O）] 2+（1R ; bpy = 2,2'-联吡啶，Rtpy = 2,2'：6'，2''-叔吡啶衍生物）配合物合成并表征了Rtpy上的4'-取代基，以揭示取代基对其结构，理化性质和对水氧化的催化活性的影响。1R的几何结构不受Rtpy上4'取代基的供电子能力影响。对于1R观察到类似的多步质子偶联电子转移反应并且，随着取代基的供电子能力的增加，每个氧化步骤的氧化还原电势趋于降低，这可以解释为供电子基团在Ru中心的电子密度增加，从而稳定了积聚的正电荷。在氧化时。这与由于Ru中心的d轨道能级增加而分配给1R的金属到配体电荷转移跃迁的480 nm附近吸收带的红移一致。然而，水氧化催化反应的1R转换频率（k O 2）很大程度上取决于Rtpy配体，范围从0.05×10 –2到44×10 –2 s –1（因为观察到R =乙氧基的最高k O 2）是880倍。4'-取代
• 4,4′′′′-Azobis[2,2′: 6′,2″-terpyridine] and its Metal Complexes
  作者：Reza-Ali Fallahpour、Markus Neuburger

  DOI：10.1002/1522-2675(20010321)84:3<715::aid-hlca715>3.0.co;2-t

  日期：2001.3.21

  By two different routes, 4,4′′′′-azobis[2,2′: 6′,2″-terpyridine] was synthesized. Its ruthenium complexes show interesting metal-to-ligand charge transfer (MLCT) absorption maxima in the electronic spectra. They represent the first ruthenium complexes of terpyridine units to give blue solutions.

  通过两种不同的路线，合成了4,4''''-偶氮二[2,2': 6',2''-三联吡啶]。其钌配合物在电子光谱中显示出有趣的金属-配体电荷转移 (MLCT) 吸收最大值。它们代表了第一个产生蓝色溶液的三联吡啶单元的钌配合物。
• Structural, electronic and acid/base properties of [Ru(tpy)(tpyOH)]2+ and [Ru(tpyOH)2]2+ (tpy=2,2′:6′,2″-terpyridine, tpyOH=4′-hydroxy-2,2′:6′,2″-terpyridine)
  作者：Kent A. Maghacut、Alessa B. Wood、Walter J. Boyko、Timothy J. Dudley、Jared J. Paul

  DOI：10.1016/j.poly.2013.09.029

  日期：2014.1

  such a system would work, interactions between the ligand and metal in the varying protonation states must be studied. In this work, we have synthesized para-hydroxyl-substituted terpyridine complexes of ruthenium, [Ru(tpy)(tpyOH)]2+ and [Ru(tpyOH)2]2+ (tpy = 2,2′:6′,2″-terpyridine, tpyOH = 4′-hydroxy-2,2′:6′,2″-terpyridine), to determine how the protonation state affects the electronic properties of the

  通过选择具有多个质子化态的配体来开发pH可转换金属催化剂将是一个有用的设计原则。为了更好地理解这样的系统如何工作，必须研究在不同质子化状态下配体与金属之间的相互作用。在这项工作中，我们合成了钌，[Ru（tpy）（tpyOH）] 2+和[Ru（tpyOH）2 ] 2+的对羟基取代的联吡啶配合物。（tpy = 2,2'：6'，2''-吡啶，tpyOH = 4'-羟基-2,2'：6'，2''-吡啶），以确定质子化态如何影响配合物的电子性质使用紫外可见光谱和计算技术。此外，我们研究了这些配合物的电化学和结构性质。当处于质子化状态时，这两种络合物在可见光区域都会产生标准的金属到配体电荷转移（MLCT）电子跃迁。然而，当去质子化时，观察到从由金属d和去质子化吡啶鎓配体轨道的混合物组成的填充分子轨道到空的配体轨道的新电子跃迁。这些过渡被称为金属-配体到配体的混合电荷转移（M mix LCT）。在去质子化的[Ru（TPY）（tpyO
• Conventional and metal-directed synthesis of homodinuclear and heterotrinuclear complexes of homoditopic and heteroditopic ligands incorporating bpy and tpy metal-binding domains
  作者：Edwin C. Constable、Peter Harverson、Catherine E. Housecroft、Ebbe Nordlander、Jerry Olsson

  DOI：10.1016/j.poly.2005.07.007

  日期：2006.1

  Strategies for the preparation of multinuclear complexes containing homoditopic and heteroditopic ligands based upon 2,2$-bipyridine (bpy) and 2,2:6$,2$$-terpyridine metal binding domains are presented. Both conventional approaches based upon preparation of a free ligand and subsequent coordination and metal-directed reactions of coordinated ligands are utilized in the various strategies. A representative series of complexes of these ligands has been prepared. (c) 2005 Elsevier Ltd. All rights reserved.
• Complexes of the Ruthenium(II)-2,2':6',2''-terpyridine Family. Effect of Electron-Accepting and -Donating Substituents on the Photophysical and Electrochemical Properties
  作者：Mauro Maestri、Nicola Armaroli、Vincenzo Balzani、Edwin C. Constable、Alexander M. W. Cargill Thompson

  DOI：10.1021/ic00114a039

  日期：1995.5

  We have investigated the luminescence properties of 14 [Ru(tpy-X)(tpy-Y)](2+) complexes (tpy = 2,2':6',2''-terpyridine; X = Y = MeSO(2), Cl, H, Ph, EtO, OH, or Me(2)N; X = H, Y = MeSO(2); X = OH, Y = MeSO(2); X = Cl, Y = EtO; X = OH, Y = Ph; X = MeSO(2), Y = Me(2)N; X = Cl, Y = Me(2)N; X = OH, Y = Me(2)N; Me CH3; Et = C2H5; Ph = C6H5). All the complexes examined display a strong luminescence in rigid matrix at 77 K, with lifetimes in the 1-10 mu s time scale. The energy of the emission maximum is red shifted for both electron-accepting and electron-donating substituents compared to that of the parent Ru(tpy)(2)(2)+ complex. At room temperature, electron-accepting substituents increase the luminescence quantum yield and the excited state lifetime, whereas electron-donating substituents show an opposite effect. The temperature dependence of the emission lifetime has been investigated for some representative complexes, and the role played by activated and activationless nonradiative transitions is examined. It is shown that the values of rate constants for radiationless decay from the luminescent excited state to the ground state are governed not only by the energy gap but also by the nature of the substituents, which presumably affects the changes in the equilibrium displacement or frequency between the two levels: Correlations of the electrochemical redox potentials, the Hammett sigma parameter, and the energy of the luminescent level are reported and discussed. Such correlations show that electron-accepting substituents have a larger stabilization effect on the LUMO pi* ligand-centered orbital than on the HOMO pi(t(2g)) metal orbital, whereas electron-donating substituents cause a larger destabilization on the HOMO pi(t(2g)) metal orbital than on the LUMO pi* ligand-centered orbital. Heteroleptic complexes carrying an electron-accepting group and an electron-donating group always show lower emission energies when compared with the parent homoleptic complexes because the pi* orbital of the tpy-A Ligand is stabilized, and the tpy-D ligand destabilizes the metal-centered pi(t(2g)) orbitals.