[Os(4,7-dimethyl-1,10-phenanthroline)2Cl2] | 220062-46-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: [Os(4,7-dimethyl-1,10-phenanthroline)2Cl2]
• 英文别名: dichloroosmium;4,7-dimethyl-1,10-phenanthroline
• CAS: 220062-46-4
• 化学式: C₂₈H₂₄Cl₂N₄Os
• 分子量: 677.631
• InChiKey: DKRNAWJTMDEPSP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  4,7-二甲基-1,10-菲咯啉 、 [Os(4,7-dimethyl-1,10-phenanthroline)2Cl2] 以 乙醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  热活化、反转界面电子转移动力学：氧化锡纳米粒子与静电结合分子反应物之间的高驱动力反应

  摘要：

  已经通过瞬态吸收光谱检查了氧化锡纳米颗粒与静电结合的 Os(III) 和 Ru(III) 配合物之间快速电子转移 (ET) 的动力学和机制。反应顺序研究表明，至少在短时间内，电子直接从氧化锡导带转移，而不是通过局部氧化还原陷阱态。反应发生在高驱动力范围内（ΔG = -1.1 至 -2.3 eV）并跨越 Marcus 正常区域、无障碍区域和倒置区域。（倒反应性，虽然在均相溶液相反应中很常见，但在界面反应中很少观察到。）根据反应物，正常或倒转的动力学行为也可以通过 pH 诱导的导带边缘能量操纵和， 所以，整体反应驱动力。在如此广泛的驱动力范围内对动力学解析的 ET 的观察允许对重组能量进行评估...

  DOI：

  10.1021/ja0024744

文献信息

• Dipyridophenazine Complexes of Os(II) as Red-Emitting DNA Probes:  Synthesis, Characterization, and Photophysical Properties
  作者：R. Erik Holmlin、Johanna A. Yao、Jacqueline K. Barton

  DOI：10.1021/ic9808955

  日期：1999.1.1

  Polypyridyl complexes of Os(II) bearing one dipyridophenazine (dppz) derivative and two ancillary ligands derived from bipyridine (bpy) or phenanthroline (phen) exhibit emission maxima at similar to 740 nm and average excited-state lifetimes in the 10 ns range upon binding to DNA by preferential intercalation of the dppz ligand. A family of [Os(L-1)(L-2)(L-3)](2+) and [Os(L-1)(2)(L-2)](2+) complexes with simple modifications in the ancillary phen or bpy ligands (L-1 and L-3) as well as the intercalating dppz ligand (L-2) was prepared. By cyclic voltammetry, electron-donating substituents on the ancillary ligands lowered the Os(3+/2+) reduction potential but did not affect the reduction potential of the dppz ligand. A methyl substituent at the 7-, 8-, or 6-position of the dppz ligand shifted the phenazine reduction toward the negative but did not affect the Os(3+/2+) potential. Absorption titrations indicated intercalative binding to DNA with high affinity (K-B similar to 10(6) M-1) for the family of complexes, although at high ratios (50:1) of base pairs to metal, complexes with ancillary 4,7-dimethylphenanthroline or 4,4'-dimethylbipyridine ligands exhibit less hypochromism (26-27%) in the pi-pi* transition on the dppz ligand compared to complexes with 5,6-dimethylphenanthroline (30-37%) or the parent phen (31-35%). By steady-state and time-resolved emission spectroscopy, complexes bound to DNA by intercalation with substituents on the 4,7- or 4,4'-positions of the ancillary phen or bpy displayed lower quantum yields for emission (Phi(em)) compared to complexes with the parent phen, while complexes with methyl substituents on the dppz ligand had the greatest Phi(em). Studies with poly d(AT), poly d(GC), and mixed-sequence DNA revealed that the emission yields are also sequence-dependent. Comparative luminescence studies in CH2Cl2 demonstrated that these effects arise from a combination of (i) the inherent sensitivity of the excited state to ligand structure and (ii) perturbations in DNA binding geometry introduced by substituents on the ancillary and intercalating ligands. Our results clarify the relationships between ligand architecture and emission yield and lifetime in the presence and absence of DNA and illustrate the utility of dppz complexes of Os(II) as luminescent probes for DNA.