| 136892-03-0

• CAS: 136892-03-0
• 化学式: C₈₁H₇₈N₁₀RuS₂*4F₆P
• 分子量: 1936.64
• InChiKey: ZBVRWASMRRWDIE-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  bis(4-methyl-4'-(4-(N-phenothiazinato)butyl)-2,2'-bipyridine)dichlororuthenium(II) 、 {423-DQ(2+)}{PF6}2 在 ammonium hexafluorophosphate 作用下， 以 乙二醇 为溶剂， 以28%的产率得到
  参考文献：
  名称：

  Charge separation in linked tris(2,2'-(bipyridine)-ruthenium donor-acceptor complexes

  摘要：

  Time-resolved emission studies have been performed on a series of covalently linked Ru(bipyridine)3-donor-acceptor complexes. In these complexes the donor is a phenothiazine moiety linked to a bipyridine by a (-CH2-)4 chain, and the acceptor is an N,N'-diquaternary-2,2'-bipyridinium moiety, linked to a bipyridine by a (-CH2-)2 chain. Excitation to the Ru(bipyridine)3 metal-to-ligand charge-transfer (MLCT) state leads to a long-lived charge-separated state. The results are compared to those obtained in the analogous Ru(bipyridine)3-acceptor complexes. The results can be understood in terms of a model in which the initial step in the formation of the charge-separated state is oxidative quenching of the MLCT state, followed by phenothiazine to ruthenium electron transfer. The charge separation occurs efficiently in dichloroethane, but not in acetonitrile. This result is discussed in terms of the relative rates of acceptor-to-ruthenium reverse electron transfer in the two solvents.

  DOI：

  10.1021/j100179a034

文献信息

• Photochemically induced charge separation at the molecular level. A chromophore-quencher complex containing both an electron donor and an acceptor
  作者：Earl Danielson、C. Michael Elliott、Jon W. Merkert、Thomas J. Meyer

  DOI：10.1021/ja00242a050

  日期：1987.4

  chromophore-quencher complexes where following optical excitation of a metal-to-ligand charge transfer (MLCT) or a porphyrin ..pi.. ..-->.. ..pi..* chromophore, oxidative or reductive intramolecular electron-transfer quenching occurs. In a recent example, photolysis of a porphyrin-based system containing both an electron-transfer donor and an acceptor led to a relatively long-lived (3 ..mu..s) photoinduced

  已知发色团-猝灭剂复合物的例子，其中在金属到配体电荷转移 (MLCT) 或卟啉 ..pi....-->.. ..pi..* 发色团，氧化性或还原性的光学激发之后发生分子内电子转移猝灭。在最近的一个例子中，包含电子转移供体和受体的基于卟啉的系统的光解导致相对长寿命 (3 μs) 的光诱导电荷分离到外围供体和受体氧化还原位点上，其中储存的氧化还原电位，..delta..G/sup 0/ > 1.0 eV。这种系统的一个价值是它们开始揭示氧化和还原等效物是如何通过光化学产生并储存在同一分子中的。他们在此报告称，基于 MLCT 的复合物 (Ru(Me(bpy)-3DQ/sup 2 +/)(Me(bpy)-PTZ)/sub 2/)/sup 4 +/ 的激发之后是一系列基于 PTZ 和 -DQ/sup 2 +/ 氧化还原位点以相对高的效率导致电荷分离状态的分子内事件，其瞬时存储的自由能约为 ..delta
• Charge Separation in Donor-Chromophore-Acceptor Assemblies: Linkage and Driving Force Dependence of Photoinduced Electron Transfers
  作者：S. L. Larson、C. Michael Elliott、D. F. Kelley

  DOI：10.1021/j100017a038

  日期：1995.4

  A series of covalently linked Ru(bipyridine)(3)-donor-acceptor complexes was prepared where the donor-to-chromophore and acceptor-to-chromophore methylene chain lengths were varied. Time-resolved absorption studies were performed to elucidate intramolecular electron transfer rates. The electron donor in the above series is a phenothiazine moiety Linked to a bipyridine by a (-CH2-)(p), p = 3-8 chain, and the electron acceptor is an N,N'-diquaternary-2,2'-bipyridinium moiety Linked to a bipyridine by a (-CH2-)(m), m = 2, 3, 4 chain. Oxidative quenching of the Ru(bipyridine)(3) metal-to-ligand charge transfer (MLCT) state followed by phenothiazine-to-ruthenium electron transfer resulted in a long-lived charge-separated state. A wavelength-dependent excitation resulted in a slowly decaying absorption which is assigned to the excited-state phenothiazine. The magnitude of this component in the transient absorption serves as an internal standard for determining relative quantum yield for formation of the charge-separated state. Marcus inverted region behavior was observed in back electron transfer. Rate constants for electron transfer from phenothiazine to Ru(III) decreased as the length of the bridging chain increased from p = 4 to 8. Chain length independence of the back electron transfer rate in the series of complexes with varied chromophore-acceptor distances (m = 2, 3, and 4) suggests the formation of an association complex during oxidative quenching of MLCT state and argues against a sigma-bond superexchange pathway for back electron transfer.