Zn(octaethylporphyrin-d4) | 61918-69-2

• 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: Zn(octaethylporphyrin-d4)
• CAS: 61918-69-2
• 化学式: C₃₆H₄₄N₄Zn
• 分子量: 602.13
• InChiKey: VVUVWOLOUOYXOI-WIWXDABZSA-N

反应信息

• 作为反应物：
  描述：

  Zn(octaethylporphyrin-d4) 在 tetrabutylammonium hexafluorophosphate 作用下， 以 further solvent(s) 为溶剂， 生成 Zn octaethylporphyrin-d4(1-)(radical)
  参考文献：
  名称：

  游离碱和八乙基卟啉锌（II）阴离子的共振拉曼光谱

  摘要：

  Resonance Raman (RR) spectra are reported for the anions of thc OEP, Zn(OEP)-, and the meso-deuteriated isotopomers, OEP-d4- and Zn(OEP-d4)-, (OEP = octacthylporphyrin). In general, the RR spectra of Zn(OEP)- are similar to those of thc parent neutral. The RR enhancement patterns, band polarizations, and meso-deuteriation shifts give no evidence of a static Jahn-Teller distortion in this anion. Reduction does, however, alter the structure of the macrocycle, as is evidenced by shifts in the frequencies of certain skeletal modes. The largest shifts are observed in vibrations involving the C(a)N bonds. Reduction also affects the C(a)C(m) bonds but to a lesser extent. In contrast, the C(b)C(b) bonds are virtually unaffected. The observed pattern of reduction-induced shifts is different than that predicted on the basis of the structure of the e(g)* orbital in which the unpaired electron resides. The altered electron density is attributed to the presence of the Zn(II) ion which concentrates the excess density on atoms near the positive core. In the case of the free base porphyrin, the RR spectra of the anion are quite different from those of the neutral. In particular, non-totally symmetric vibrations exhibit strong RR activity in the anion, whereas none is observed for the neutral. This RR activity is attributed to vibronic coupling between the ground electronic state and the low-lying B3g excited state that is present in the anion. The reduction-induced frequency shifts of thc skeletal modes of the free base are also different from those of the Zn(II) complex. For OEP, the largest shifts arc observed in vibrations involving the C(a)C(m) and C(b)C(b) bonds where little shift is observed in modes involving the C(a)N bonds. These data suggest that the excess electron density in OEP- is concentrated in the periphery of the macrocycle and lend support to the idea that the metal ion attracts the excess density in Zn(OEP)-.

  DOI：

  10.1021/j100191a016

文献信息

• Electronic structure of metalloporphyrin π-anions
  作者：G.P. Gurinovich、I.F. Gurinovich、N.V. Ivashin、G.N. Sinyakov、A.M. Shulga、S.N. Terekhov、I.V. Filatov、K. Dzilinski

  DOI：10.1016/0022-2860(88)87026-1

  日期：1988.2

  characteristic changes in all the spectra and in the charge distribution. Hyperfine splitting in the ESR spectra of anion radicals of zinc complexes of monoaza- and diazaetioporphyrins is detected. ESR spectra are simulated on the basis of McConnel and Chesnut's relation and unpaired electron distribution. In 1 H NMR spectra of dianions large upfield shifts of proton signals under the influence of paramagnetic

  摘要 通过电子吸收光谱、ESR、1 H 和 13 C NMR、IR 和拉曼光谱研究了金属卟啉分子在金属卟啉溶液与 Na 和 K 金属接触过程中转化为单-和双-π-阴离子的过程。电荷分布通过 CNDO/2 方法计算。结果表明，阴离子的产生伴随着所有光谱和电荷分布的特征变化。检测到单氮杂和重氮杂卟啉的锌配合物的阴离子自由基的 ESR 光谱中的超精细分裂。ESR 谱是根据 McConnel 和 Chesnut 的关系和不成对电子分布模拟的。在双阴离子的 1 H NMR 谱中，观察到在顺磁环电流的影响下质子信号的大上场位移。中性卟啉的 13 C 化学位移与电荷分布相关，而相应的二价阴离子的化学位移由平均激发能、顺磁环电流和电子密度的变化决定。IR 和拉曼光谱的大部分波段在传递给阴离子时会发生低频偏移。综合分析揭示了分子特定键和整个电子结构变化的定性图片。这些数据通过二价阴离子中电子密度的量子化学计算得到证实。IR