Ni(2,3,6,7,12,13,16,17-octaethylporphycene) | 130351-27-8

• 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: Ni(2,3,6,7,12,13,16,17-octaethylporphycene)
• CAS: 130351-27-8
• 化学式: C₃₆H₄₄N₄Ni
• 分子量: 591.462
• InChiKey: YBQXIYUSBWKVQA-FLNDASQWSA-N

反应信息

• 作为反应物：
  描述：

  Ni(2,3,6,7,12,13,16,17-octaethylporphycene) 、 tris(acetonitrile)pentamethylcyclopentadienylruthenium(II) hexafluorophosphate 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  金属卟啉：（五甲基环戊二烯基）钌和 π 配合物的合成和表征

  摘要：

  史无前例的卟啉配合物，包含 [RuCp*]（Cp*：五甲基环戊二烯基）片段，位于中央 N(4) 核心或直接与大环的“pi 面”结合，并已制备并充分表征，包括通过单晶X 射线衍射分析。详细检查了这些新化合物家族的光学和电化学特性，揭示了寿命已确定的“坐在顶部”复合物的荧光。对于具有“稠合”钌茂部分的两种金属（M = Cu，Ni）卟啉衍生物，通过激光闪光光解后从钌茂单元到大环的有效光诱导电子转移，观察到强电子通讯，提供电荷分离状态。通过在单电子氧化物种的 EPR 光谱中观察到强自旋-自旋耦合，也证实了这种钌茂 - 大环通讯。这允许计算两个金属中心之间的距离。

  DOI：

  10.1021/ja905284d
• 作为产物：
  描述：

  nickel(II) acetate tetrahydrate 、 2,3,6,7,12,13,16,17-octaethylporphycene 以 N,N-二甲基甲酰胺 为溶剂， 以90%的产率得到Ni(2,3,6,7,12,13,16,17-octaethylporphycene)
  参考文献：
  名称：

  Electrochemical, UV/Visible, and EPR Characterization of Metalloporphycenes Containing First-Row Transition Metals

  摘要：

  Porphycenes containing d(4) to d(10) first-row transition-metal ions are characterized by electrochemical, UV-visible spectroelectrochemical, and EPR measurements. The investigated compounds are represented by (OEPc)M where M = Co(II), Ni(II), Cu(II), or Zn(lI) and (OEPc)MCl where M = Mn(III) or Fe(III) and OEPc is the dianion of 2,3,6,7,12,13,16,17-octaethylporphycene. The metalloporphycenes exhibit electrochemical properties which are different upon reduction as compared to the corresponding metalloporphyrins, and this is attributed to the different symmetry (D-2h) and smaller cavity size of the porphycene ring. The HOMO-LUMO gap in the metalloporphycenes is nearly 400 mV smaller than in related complexes of (P)M(II) where P is the dianion of octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP). However, like the porphyrins, the energy separation in the HOMO-LUMO gap of the porphycenes varies as a function of the size and electronegativity of the central metal ion. Electrochemical and EPR data on singly-reduced [(OEPc)M] show no evidence for the formation of a metal(I) oxidation state, and this is also the conclusion from analysis of the redox potentials. EPR spectra of electrogenerated [(OEPc)Zn](+.) and [(OEPc)Ni](+.) suggest the formation of an A(u)-type radical but with possible mixing of the closely-separated b(1u) orbitals. UV-visible data were used to verify several theoretical predictions, and an MO diagram is presented for the interpretation of the spectroscopic data.

  DOI：

  10.1021/j100097a014