bis(2,3,7,8,12,13,17,18-octaethylporphyrinato)hafnium(IV)(1+) | 132017-19-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: bis(2,3,7,8,12,13,17,18-octaethylporphyrinato)hafnium(IV)(1+)
• CAS: 132017-19-7
• 化学式: C₇₂H₈₈HfN₈
• 分子量: 1244.03
• InChiKey: WKWBAXDECKGCKU-OPOWQWKYSA-N

反应信息

• 作为反应物：
  描述：

  bis(2,3,7,8,12,13,17,18-octaethylporphyrinato)hafnium(IV)(1+) 以 二氯甲烷 为溶剂， 生成 bis(2,3,7,8,12,13,17,18-octaethylporphyrinato)hafnium(IV)(2+)
  参考文献：
  名称：

  Buchler, Johann W.; Cian, Andre De; Elschner, Steffen, Chemische Berichte, 1992, vol. 125, # 1, p. 107 - 116

  摘要：

  DOI：
• 作为产物：
  描述：

  bis(2,3,7,8,12,13,17,18-octaethylporphyrinato)hafnium(IV) 以 二氯甲烷 为溶剂， 生成 bis(2,3,7,8,12,13,17,18-octaethylporphyrinato)hafnium(IV)(1+)
  参考文献：
  名称：

  Buchler, Johann W.; Cian, Andre De; Elschner, Steffen, Chemische Berichte, 1992, vol. 125, # 1, p. 107 - 116

  摘要：

  DOI：

文献信息

• Spectroscopic characterization of zirconium(IV) and hafnium(IV) sandwich porphyrin complexes
  作者：Paul C. Martin、John Arnold、David F. Bocian

  DOI：10.1021/j100109a014

  日期：1993.2

  Optical, infrared (IR), and resonance Raman (RR) spectra are reported for the sandwich porphyrins Zr(OEP)2 and Hf(OEP)2 (OEP = octaethylporphyrin) and their respective mono- and dication radicals. For comparison, absorption and vibrational data were also obtained for representative neutral and oxidized monomeric Zr(IV) and Hf(IV) complexes. The vibrational data for both the monocations (all complexes) and dications (sandwich complexes only) indicate that the electrons are removed from an a1u-like molecular orbital. Consequently the ground states of the singly and doubly oxidized compounds are 2A1u and 1A1g, respectively. The C(b)C(b) stretching vibrations are found to be the most reliable indicators of oxidation. These modes exhibit almost linear upshifts upon successive oxidations of the porphyrin rings. On the basis of the shift-pattern exhibited by the IR oxidation-marker bands of the Zr(IV) and Hf(IV) species, the oxidation-marker band of MOEP complexes is identified as the nu38 (C(b)C(b)) stretching mode. In the course of the RR studies of the sandwich complexes, experiments were performed in which the excitation energy is resonant with the new electronic states that arise due to the strong pipi interactions in these assemblies. These include the Q' and Q'' states of the neutral species and the near-IR charge-resonance states of the cations. No RR scattering is observed upon excitation into either the Q' or Q'' absorptions. In contrast, excitation into the near-IR absorptions of the mono- and dications results in RR scattering from out-of-plane deformations of the porphyrin rings. The resonance enhanced out-of-plane deformations appear to be symmetrical linear combinations of porphyrin monomer vibrations rather than intradimer vibrations (modes that arise due to the additional degrees of freedom present in the dimer versus the two independent monomers). Collectively, the studies of the neutral and oxidized M(OEP)2 complexes provide further insights into the effects of strong pipi interactions and the consequences of ring-based oxidations in porphyrinic systems.