nickel(II) meso-(β-cyanoethenyl)-2,3,7,8,12,13,17,18-octaethylporphyrin | 164863-69-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: nickel(II) meso-(β-cyanoethenyl)-2,3,7,8,12,13,17,18-octaethylporphyrin
• CAS: 164863-69-8
• 化学式: C₃₉H₄₅N₅Ni
• 分子量: 642.51
• InChiKey: RBTNTCACPOWPNP-USTLXUFHSA-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

• 作为产物：
  描述：

  2,3,7,8,12,13,17,18-OCTAETHYL-21H,23H-PORPHINE NICKEL(II) 在 POCl₃ 、 NaH 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 生成 nickel(II) meso-(β-cyanoethenyl)-2,3,7,8,12,13,17,18-octaethylporphyrin
  参考文献：
  名称：

  Spectroscopic Determination of Proton Position in the Proton-Coupled Electron Transfer Pathways of Donor−Acceptor Supramolecule Assemblies

  摘要：

  A homologous set of porphyrin derivatives possessing an isocyclic five-membered ring appended with an amidinium functionality has been used to examine proton-coupled electron transfer (PCET) through well-characterized amidine-carboxylic acid interfaces. Conjugation between the porphyrin chromophore and the amidinium interface can be altered by selective reduction of the isocyclic ring of an amidinium-purpurin to produce an amidinium-chlorin. The highly conjugated amidinium-purpurin displays large spectral shifts in the visible region upon alteration of the amidinium/amidine protonation state; no such change is observed for the chlorin homologue. Analysis of the UV-vis absorption and emission profiles of the amidinium-purpurin upon deprotonation allows for the measurement of the porphyrinic-amidinium acidity constant for the ground state (pK(a) = 9.55 +/- 0.1 in CH3CN) and excited state (pK(a)* = 10.40 +/- 0.1 in CH3CN). The absorption spectrum of the purpurin also provides a convenient handle for determining the protonation state of assembled interfaces. In this way, the purpurin macrocycle provides a general tool for PCET studies because it can be used to determine the location of a proton within PCET interfaces formed from carboxylic acid electron acceptors including dinitrobenzenes (DNBs) and naphthalenediimide (NI), which have been used extensively in previous PCET studies. An amidine-carboxylic acid interface is observed for electron-rich acceptors, whereas the ionized amidinium- carboxylate interface is observed for electron-poor acceptors. The PCET kinetics for purpurin/chlorin associated to NI are consistent with an amidine-carboxylic acid interface, which is also verified spectrally.

  DOI：

  10.1021/ja062430g