nickel(II) tetraphenylporphyrin-bispiperidine | 55835-67-1

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: nickel(II) tetraphenylporphyrin-bispiperidine
• 英文别名: Ni(meso-5,10,15-20-tetraphenylporphyrinate)(piperidine)2；nickeltetraphenylporphyrin-(piperidine)2
• CAS: 55835-67-1
• 化学式: C₅₄H₅₀N₆Ni
• 分子量: 841.721
• InChiKey: PLJKCCOUJUTYSO-NBICUONBSA-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

• 作为反应物：
  描述：

  nickel(II) tetraphenylporphyrin-bispiperidine 以 further solvent(s) 为溶剂， 生成 5,10,15,20-tetraphenylporphinatonickel(II)
  参考文献：
  名称：

  Probing transient molecular structures with time-resolved pump/probe XAFS using synchrotron X-ray sources

  摘要：

  Laser pulse pump, X-ray pulse probe X-ray absorption fine structure (pump-probe XAFS) experiments using synchrotron sources are described from technical considerations and from scientific significance. There are three technical challenges of such experiments: (1) laser photoexcitation, (2) synchronization of laser pulse and X-ray pulse, and (3) detection; each of which is investigated in detail. Based on the results from these investigations, the transient molecular structure of a reaction intermediate produced by photoexcitation of NiTPP-L-2 (NiTPP, nickeltetraphenylporphyrin; L, piperidine) in solution has been captured for the first time with the pump-probe XAFS on a 14-ns time scale obtained from the X-ray pulses from a third generation synchrotron source. The experimental results confirm that photoexcitation leads to the rapid removal of both axial ligands to produce a transient square-planar intermediate, NiTTP, with a lifetime of 28 ns. The transient structure of the photodissociated intermediate is nearly identical to that of the ground state NiTPP, suggesting that the intermediate adopts the same structure as the ground state in a non-coordinating solvent before it recombines with two ligands to form the more stable octahedrally coordinated NiTPP-L-2. No detectable population of a penta-coordinated intermediate was present. This experiment demonstrates the feasibility of determining transient molecular structures in disordered media using the temporal resolution of a synchrotron X-ray source. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0368-2048(01)00289-4

文献信息

• Laser-induced excited-state ligation changes for nickel tetraphenylporphine monitored by Raman spectroscopy
  作者：Dongho. Kim、Thomas G. Spiro

  DOI：10.1021/ja00268a065

  日期：1986.4

  hole created in d/sub z /sup 2// orbital. It should therefore be possible to shift the equilibrium between 4- and 6-coordinate species with photons. In this report the authors demonstrate such pumping with CW laser excitation of stationary samples of NiTPP (nickel tetraphenylporphine) in pyridine and piperidine, using resonance Raman (RR) spectroscopy to monitor the ligation changes. The RR spectra

  金属卟啉提供了一种有趣的可能性，即通过从最初填充的卟啉..pi..-..pi..* 状态跨越系统间，经历与激发配体场状态泵浦相关的轴向连接变化。一个例子是血红素蛋白的 CO 加合物的极其快速和有效的光解离，它已被广泛用于研究这些 O/sub 2/-携带和激活大分子的血红素相关蛋白质动力学。镍卟啉为研究提供了一个有吸引力的系统，因为它们在非配位和弱配位溶剂中是 4 配位和低自旋，但在强配位溶剂中是 6 配位和高自旋。Holten 及其同事用瞬态光谱学表明，6 配位物质的可及激发态（低自旋）迅速失去其轴向配体，而 4 配位镍卟啉（高自旋）的激发态则被连接，感谢到在 d/sub z /sup 2// 轨道中创建的孔。因此，应该有可能用光子改变 4 和 6 坐标物种之间的平衡。在本报告中，作者使用共振拉曼 (RR) 光谱来监测连接变化，证明了在吡啶和哌啶中的 NiTPP（镍四苯基卟啉）固定样品的连续激光激发的这种泵浦。RR