nickel(II) 5-(amidinium)ethynyl-10,15,20-trimesitylporphyrin chloride | 956428-36-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: nickel(II) 5-(amidinium)ethynyl-10,15,20-trimesitylporphyrin chloride
• CAS: 956428-36-7
• 化学式: C₅₀H₄₅N₆Ni*Cl
• 分子量: 824.091
• InChiKey: XYVZUCWKTMETST-ORUZJWGBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  5-bromo-10,15,20-trimesitylporphyrin 在 PdCl₂(PPh₃)2 、 CuI 、 Et₃N 、 K₂CO₃ 、 n-BuLi 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成 nickel(II) 5-(amidinium)ethynyl-10,15,20-trimesitylporphyrin chloride
  参考文献：
  名称：

  Structurally Homologous β- and meso-Alkynyl Amidinium Porphyrins

  摘要：

  Alkynylamidinium groups have been introduced at the beta and meso positions of a nickel(II) porphyrin (PNi(II)) framework. The modification permits the distance between the amidinium-amidine acid-base group and porphyrin to be increased while effectively maintaining pi conjugation between the porphyrin macrocycle and the acid-base functionality. Use of an ethynyl spacer as a linker (i) extends the amidinium functionality away from the sterically bulky mesityl groups of the porphyrin, allowing it to be nearly planar with respect to the porphyrin ring, and (ii) draws the pi-orbital character of the porphyrin out toward the amidinium functionality, thereby engendering sensitivity of the electronic properties of the porphyrin macrocycle to the protonation state of the amidinium. The barrier for rotation of the amidinium group, as calculated by time-dependent density functional theory (TDDFT), is similar to 8.5kT (5 kcal/mol) for both porphyrins. Analysis of UV-visible absorption profiles for the beta- and meso-alkynylamidinium PNi(II) upon deprotonation enables accurate determination of the amidinium acidity constants for the ground state (pK(a)(beta) = 7.03 +/- 0.1, pK(a)(meso) = 7.74 +/- 0.1 in CH3CN) and excited state (pK(a)(*)(beta) = 6.89 +/- 0.1, pK(a)(*)(meso) = 8.37 +/- 0.1 in CH3CN) porphyrins. Whereas pK(a)(*) < pK(a) for the beta-alkynylamidinium porphyrin, pK(a)(*) > pK(a) for the meso-alkynylamidinium porphyrin, indicating that beta-alkynylamidinium PNi(II) is a photoacid and meso-alkynylamidinium PNi(II) is a photobase. These divergent behaviors are supported by analysis of the frontier molecular orbitals of the homologous pair with TDDFT.

  DOI：

  10.1021/ic700838s