2,3,9,10,16,17,23,24-octakis(3,3-dimethyl-1-butynyl)phthalocyanine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 2,3,9,10,16,17,23,24-octakis(3,3-dimethyl-1-butynyl)phthalocyanine
• 英文别名: 6,7,15,16,24,25,33,34-Octakis(3,3-dimethylbut-1-ynyl)-2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13(18),14,16,19(39),20,22(27),23,25,28(38),30(37),31(36),32,34-nonadecaene；6,7,15,16,24,25,33,34-octakis(3,3-dimethylbut-1-ynyl)-2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13(18),14,16,19(39),20,22(27),23,25,28(38),30(37),31(36),32,34-nonadecaene
• 化学式: C₈₀H₈₂N₈
• 分子量: 1155.58
• InChiKey: UFHFSCFFBSANJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  22.9
• 重原子数：
  88
• 可旋转键数：
  16
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  109
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,9,10,16,17,23,24-octakis(3,3-dimethyl-1-butynyl)phthalocyanine 、 cobalt(II) chloride 在 Li 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 以51%的产率得到[2,3,9,10,16,17,23,24-octa(3,3-dimethyl-1-bytynyl)phthalocyaninato]cobalt(II)
  参考文献：
  名称：

  Aggregation Effects on Electrochemical and Spectroelectrochemical Properties of [2,3,9,10,16,17,23,24-Octa(3,3-dimethyl-1-butynyl)phthalocyaninato]cobalt(II) Complex

  摘要：

  我们制备了标题复合物 [Co(odmbpc)]，并在二氯甲烷溶液中对其进行了电化学和光谱电化学研究。这种复合物在浓度约为 6 × 10-5 mol dm-3 时的循环伏安图在 E1/2 = -0.67 V（对二茂铁+/二茂铁）和-1.74 V 的两个可逆还原波，分别归因于以钴为中心的还原和以三键为中心（外围取代基）的还原，以及在 0.26、0.46 和 0.74 V 的三个准可逆氧化波，前两个和后一个分别归因于以酞菁-色素为中心的氧化和以钴为中心的氧化。电生成物的电子吸收光谱证实了其中一些归因。在 6 × 10-4 mol dm-3 的条件下，直到施加的电势扫到第二个还原波时，才观察到第一个还原波。然而，在相同条件下，光学透明薄层电极在第一还原波附近的电位下进行受控电位电解时，在第二还原波附近的电位下不进行任何初步电解，就会产生急剧的光谱变化。这种奇怪的现象可以从络合物在溶液中的分子聚集角度进行讨论。研究发现，外围的炔基具有轻微的电子负载性。

  DOI：

  10.1246/bcsj.71.1039
• 作为产物：
  描述：

  4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile 在 lithium amylate 作用下， 以 戊醇 为溶剂， 反应 3.0h， 以36%的产率得到2,3,9,10,16,17,23,24-octakis(3,3-dimethyl-1-butynyl)phthalocyanine
  参考文献：
  名称：

  Synthesis of 2,3,9,10,16,17,23,24-Octaalkynylphthalocyanines and the Effects of Concentration and Temperature on Their ¹H NMR Spectra

  摘要：

  The syntheses of 3,4- and 4,5-diiodophthalonitriles are described. Coupling of the latter compound with Pd(PPh(3))(2)Cl-2 and 1-octyne, 1-heptyne, 1-hexyne, 1-pentyne, and 3,3-dimethyl-1-butyne gave a series of 4,5-dialkynylphthalonitriles. Hydrogenation of 4,5-bis(1-pentynyl)phthalonitrile and 4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile gave 4,5-dipentylphthalonitrile and 4,5-bis(3,3-dimethylbutyl)phthalonitriles. Condensation of the dialkynylphthalonitriles with lithium 1-pentoxide in 1-pentanol gave 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines, while intervention of the intermediate dilithium phthalocyanines with zinc acetate gave the related zinc(II) phthalocyanines. H-1 NMR spectroscopy of these octaalkynylphthalocyanines exhibited large chemical shifts (1-2 ppm) of the internal and aromatic protons at concentrations ranging from 10(-2) to 10(-5) M and at temperatures from 27 to 147 degrees C. The effects of aggregation phenomena are discussed. The importance of reporting concentration and temperature values for NMR spectra of phthalocyanines is stressed.

  DOI：

  10.1021/jo9521662

文献信息

• Synthesis of 2,3,9,10,16,17,23,24-Octaalkynylphthalocyanines and the Effects of Concentration and Temperature on Their ¹H NMR Spectra
  作者：Dmitri S. Terekhov、Kieran J. M. Nolan、Colin R. McArthur、Clifford C. Leznoff

  DOI：10.1021/jo9521662

  日期：1996.1.1

  The syntheses of 3,4- and 4,5-diiodophthalonitriles are described. Coupling of the latter compound with Pd(PPh(3))(2)Cl-2 and 1-octyne, 1-heptyne, 1-hexyne, 1-pentyne, and 3,3-dimethyl-1-butyne gave a series of 4,5-dialkynylphthalonitriles. Hydrogenation of 4,5-bis(1-pentynyl)phthalonitrile and 4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile gave 4,5-dipentylphthalonitrile and 4,5-bis(3,3-dimethylbutyl)phthalonitriles. Condensation of the dialkynylphthalonitriles with lithium 1-pentoxide in 1-pentanol gave 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines, while intervention of the intermediate dilithium phthalocyanines with zinc acetate gave the related zinc(II) phthalocyanines. H-1 NMR spectroscopy of these octaalkynylphthalocyanines exhibited large chemical shifts (1-2 ppm) of the internal and aromatic protons at concentrations ranging from 10(-2) to 10(-5) M and at temperatures from 27 to 147 degrees C. The effects of aggregation phenomena are discussed. The importance of reporting concentration and temperature values for NMR spectra of phthalocyanines is stressed.
• Aggregation Effects on Electrochemical and Spectroelectrochemical Properties of [2,3,9,10,16,17,23,24-Octa(3,3-dimethyl-1-butynyl)phthalocyaninato]cobalt(II) Complex
  作者：Hiroaki Isago、Clifford C. Leznoff、Matthew F. Ryan、Robert A. Metcalfe、Rifka Davids、A. B. P. Lever

  DOI：10.1246/bcsj.71.1039

  日期：1998.5

  The title complex, [Co(odmbpc)], which is a single isomer and is highly soluble in common organic solvents, has been prepared and investigated electrochemically and spectroelectrochemically in dichloromethane solutions. The cyclic voltammograms of this complex at a concentration of ca. 6 × 10−5 mol dm−3 exhibited two reversible reduction waves at E1/2 = −0.67 V (vs. ferrocenium+/ ferrocene) and −1.74 V, which were attributed to cobalt-centered and triple-bond-centered (in a peripheral substituent) reductions, respectively, and three quasi-reversible oxidation waves at 0.26, 0.46, and 0.74 V, the former two and the latter one of which were attributed to phthalocyanine-chromophore-centered and cobalt-centered oxidations, respectively. Some of these assignments were supported by the electronic absorption spectra of the electro-generated species. The first reduction wave was not observed at 6 × 10−4 mol dm−3 until the applied potential was swept to the second reduction wave. Nevertheless, under the same conditions, the controlled-potential electrolyses in an optically transparent thin-layer electrode at potentials around the first reduction wave gave rise to drastic spectral changes without any preliminary electrolysis at potentials around the second reduction wave. Such strange phenomena are discussed in terms of molecular aggregation of the complexes in solutions. The peripheral alkynyl group has been found to be slightly electron-donating.

  我们制备了标题复合物 [Co(odmbpc)]，并在二氯甲烷溶液中对其进行了电化学和光谱电化学研究。这种复合物在浓度约为 6 × 10-5 mol dm-3 时的循环伏安图在 E1/2 = -0.67 V（对二茂铁+/二茂铁）和-1.74 V 的两个可逆还原波，分别归因于以钴为中心的还原和以三键为中心（外围取代基）的还原，以及在 0.26、0.46 和 0.74 V 的三个准可逆氧化波，前两个和后一个分别归因于以酞菁-色素为中心的氧化和以钴为中心的氧化。电生成物的电子吸收光谱证实了其中一些归因。在 6 × 10-4 mol dm-3 的条件下，直到施加的电势扫到第二个还原波时，才观察到第一个还原波。然而，在相同条件下，光学透明薄层电极在第一还原波附近的电位下进行受控电位电解时，在第二还原波附近的电位下不进行任何初步电解，就会产生急剧的光谱变化。这种奇怪的现象可以从络合物在溶液中的分子聚集角度进行讨论。研究发现，外围的炔基具有轻微的电子负载性。