1,4,8,11,15,18,22,25-octaethoxyphthalocyanine | 116453-75-9

• 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: 1,4,8,11,15,18,22,25-octaethoxyphthalocyanine
• 英文别名: 5,8,14,17,23,26,32,35-Octaethoxy-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-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28(38),30(37),31,33,35-nonadecaene；5,8,14,17,23,26,32,35-octaethoxy-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-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28(38),30(37),31,33,35-nonadecaene
• CAS: 116453-75-9
• 化学式: C₄₈H₅₀N₈O₈
• 分子量: 866.974
• InChiKey: PCUJOFBWLSXCHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  64
• 可旋转键数：
  16
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  183
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  1,4,8,11,15,18,22,25-octaethoxyphthalocyanine 在 三正丙胺 、 三氯硅烷 、 水 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以87%的产率得到
  参考文献：
  名称：

  Synthesis, Photochemistry, and Electrochemistry of a Series of Phthalocyanines with Graded Steric Hindrance

  摘要：

  A group of twelve new and three known silicon phthalocyanines having axial ligands and peripheral groups which provide varying amounts of steric protection to the ring face and ring periphery has been assembled. These are SiPc[OSi(n-C6H13)(3)](2), 1, (known), SiPc[OSi(i-C4H9)(2)(n-C18H37)](2), 2, SiPc(OEt)(8)[OH](2), 5, SiPc(OEt)(8)[OSi(CH3)(3)](2), 6, SiPc(OnBu)(8)[OH](2), 8, (known), SiPc(OnBu)(8)[OSi(n-C6H13)(3)](2), 9, (known), SiPc(OnBu)(8)[OSi(i-C4H9)(2)(n-C18H37)](2), 10, SiPc(dib)(4)(OnBu)(8)[OH](2), 15, SiPc(dib)(4)(OnBu)(8)[F](2), 16, SiPc(dib)(4)(OnBu)(8)[OSi(n-C6H13)(2)](2), 17, SiPc(dib)(4)(OnBu)(8)[OSi(i-C4H9)(2)(n-C18H37)](2), 18, SiPc(dib)(4)(OnBu)(8)[OSi8O12(C5H9)(7)](2), 19, SiPc(dib)(4)(OnBu)(8)[OH](2), 22, SiPc(dib)(4)(OiBu)(8)[OSi(n-C6H13)(3)](2), 23, and SiPc(dib)(4)(OiBu)(8)[OSi8O12(C5H9)(7)](2), 24. Syntheses are given for the twelve members of the group that are new. Photophysical and voltammetric investigations of six representative members of the group, 1, 2, 10, 18, 19, and 24, have been carried out. The results show that compounds 1 and 2 (no butoxy substituents at the I and 4 positions) have significantly larger values of the first oxidation potential (E+1) than those compounds (10, 18, 19, and 24) that do carry these substituents. The values of E-1 (first reduction potential) show very little in the way of structural dependence. Alkoxy substitution at the 1,4 positions affects the HOMO energies, and therefore, the addition of an electron from an electrode to the LUMO of a 1,4 substituted silicon phthalocyanine will not be a sensitive function of the substitution pattern. The removal of an electron from the HOMO in an oxidation step on the other hand would be expected to be energetically less demanding for those compounds wherein the HOMO is higher lying. This orbital energy effect of substitution makes it clear why the E+1 values for compounds 1 and 2 are significantly lower. Substitution of dibenzobarreleno (dib) at the 2,3 positions has only minor effects on the HOMO energy, as shown by the similarities in the position of the Q-band maximum. However, it is very likely that the steric effects of the dibenzobarreleno substituents and the [OSi8O12(C5H9)(7)] axial cages contribute to the observed trends in E+1. Bimolecular rate constants for quenching of the triplet states of the six target compounds by O-2, by beta-carotene, and by chloranil were measured. The first two compounds quench by triplet-triplet (TT) energy transfer, whereas the last is an electron transfer (ET) reactant. All rate parameters were sensitive to the steric crowding of the phthalocyanine pi system, but with different degrees. The least sensitive was the ET reaction with chloranil.Thus, it appears that although steric crowding of the triplet state of the silicon phthalocyanines is very effective at reducing the rate constants of exoergic electron exchange energy transfer (TT) reactions, even for a small molecule such as oxygen, it is much less effective at discriminating against electron transfer (ET) processes. These differences may be accounted for on the concept that the overlap requirement for the double electron exchange of TT energy transfer is more stringent compared to the single electron transfer (ET).

  DOI：

  10.1021/jp027006q
• 作为产物：
  描述：

  3,6-二羟基邻苯二甲腈 在 盐酸 、 lithium 、 potassium carbonate 作用下， 以 乙醇 、 水 、 丙酮 为溶剂， 反应 216.0h， 生成 1,4,8,11,15,18,22,25-octaethoxyphthalocyanine
  参考文献：
  名称：

  在五个独立的氧化还原状态中分离的同构锰酞菁系列中的可切换芳香性

  摘要：

  新型酞菁 (Pc) Mn-氮化物复合物 (OEtPc)MnN (2; OEtPc = 1,4,8,11,15,18,22,25-octaethoxy-Pc) 的合成和表征，以及它的据报道，稳定、易于获得的氧化（2+ 和 22+）和还原（2-、22-）同源物。除了开壳自由基状态 (2+, 2-) 之外，这个独特的同构系列还显示出跨越芳香族 (2)、非芳香族 (22+) 和反芳香族 (22-) 三元组的可切换芳香族特征。所有配合物都在结构上进行了表征，并在氧化还原极值 (22+, 22-) 处显示出显着的结构扭曲，与提出的 [16 或 18] 环烯 π 环电路模型一致。光谱和计算研究进一步支持这些模型。这种孤立的、完全表征的、等结构系列跨越五种氧化还原状态（22+、2+、2、2-、

  DOI：

  10.1021/jacs.8b12899

文献信息

• Synthesis, characterization, and electrochemical properties of a first-row metal phthalocyanine series
  作者：Madeline Peterson、Camden Hunt、Zongheng Wang、Shannon E. Heinrich、Guang Wu、Gabriel Ménard

  DOI：10.1039/d0dt01372b

  日期：——

  species - displaying a mix of metal- and ligand-borne redox events - was investigated and tentatively correlated to the structural properties. It was found that non-labile axial metal-ligand substituents (O2-, N3-) and the use of coordinating solvents heavily influenced the reversibility of the electrochemical events, suggesting that aggregation is a dominant consideration for well-defined electrochemical

  3d-金属酞菁系列（OEtPcM; OEtPc = 1,4,8,11,15,18,22,25-八乙氧基-酞菁; M ​​= VO，Cr，MnCl，MnN，Fe，Co，Ni ，Cu，Zn）。除OEtPcZn外，所有物种均在晶体学上进行了表征，包括质子化（OEtPcH2）和部分锂化（OEtPcHLi）前体。研究了所有物种的电化学行为-显示出金属和配体载有的氧化还原事件的混合-并初步将其与结构性质相关。发现不稳定的轴向金属-配体取代基（O2-，N3-）和配位溶剂的使用严重影响了电化学事件的可逆性，表明聚集是明确定义的电化学行为的主要考虑因素。
• Cook, Michael J.; Dunn, Adrian J.; Howe, Steven D., Journal of the Chemical Society. Perkin transactions I, 1988, p. 2453 - 2458
  作者：Cook, Michael J.、Dunn, Adrian J.、Howe, Steven D.、Thomson, Andrew J.、Harrison, Kenneth J.

  DOI：——

  日期：——
• π-Complexes of Phthalocyanines and Metallophthalocyanines
  作者：Stephen M. Contakes、Susan T. Beatty、Karen K. Dailey、Thomas B. Rauchfuss、Dieter Fenske

  DOI：10.1021/om000467i

  日期：2000.11.1

  Addition of [Cp*Ru(MeCN)(3)]PF6 to M(PcOEt) (PcOEt = octakis(ethoxy)phthalocyanine; M = H-2,H- Ni (1), Cu, VO) in dichloromethane results in the formation of Cp*Ru[eta (6)-M(PcOEt)]}PF6. The molecular structure of 1 reveals eta (6)-coordination of Cp*Ru2+ to one of the isoindole subunits of the phthalocyanine ligand. The crystal structure reveals the presence of two cofacially stacked Pc units in the asymmetric unit separated by 3.27-3.36 Angstrom. In [Cp*Ru(eta (6)-H2PcOEt)]PF6, two distinct N-H sites are apparent in the H-1 NMR and IR spectra, but only one is exchangeable. The coordinated macrocycle can be metalated. The UV and electrochemical data indicate that the pi -bonded metal center functions as an electron-donating substituent. Luminescence studies indicate that the eta (6)-coordination quenches fluorescence to a lesser degree than coordination of metals into the N-4 pocket of the phthalocyanine subunit.
• COOK, MICHAEL J.;DUNN, ADRIAN J.;HOWE, STEVEN D.;THOMSON, ANDREW J.;HARRI+, J. CHEM. SOC. PERKIN TRANS.,(1988) N 8, C. 2453-2458
  作者：COOK, MICHAEL J.、DUNN, ADRIAN J.、HOWE, STEVEN D.、THOMSON, ANDREW J.、HARRI+

  DOI：——

  日期：——
• SUBSTITUTED PHTHALOCYANINES
  申请人：Secretary of State for Defence in Her Britannic Majesty's Gov. of the United Kingdom of Great Britain and Northern Ireland

  公开号：EP0346354B1

  公开（公告）日：1992-08-19