gold(III) 5,10-di(p-hydroxyphenyl)-15,20-di(3,5-di-tert-butylphenyl)porphyrinate hexafluorophosphate | 321852-76-0

• 英文名称: gold(III) 5,10-di(p-hydroxyphenyl)-15,20-di(3,5-di-tert-butylphenyl)porphyrinate hexafluorophosphate
• CAS: 321852-76-0
• 化学式: C₆₀H₆₀AuN₄O₂*F₆P
• 分子量: 1211.09
• InChiKey: ANJZGIHVPGHLFH-LVHXYELMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.56
• 重原子数：
  74.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  94.44
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  gold(III) 5,10-di(p-hydroxyphenyl)-15,20-di(3,5-di-tert-butylphenyl)porphyrinate hexafluorophosphate 、 2,9-bis[p-(2-iodoethoxy)phenyl]-1,10-phenanthroline 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以31%的产率得到
  参考文献：
  名称：

  Multiporphyrinic Rotaxanes: Control of Intramolecular Electron Transfer Rate by Steering the Mutual Arrangement of the Chromophores

  摘要：

  A [2]-rotaxane Zn-2-Au+ made from a dumbbell component ended by Zn(II) porphyrin stoppers and a ring component incorporating a Au(III) porphyrin has been assembled in 13% yield using the transition metal templating route. H-1 NMR studies show that its:conformation in solution is very different from those of its complexes with Cu+, Ag+, and Li+. In particular, removal of the templating metal resulted in a changeover of the molecule, the threaded macrocycle undergoing a pirouetting motion placing the Au(III) porphyrin in the deft formed by the two Zn(II) porphyrin stoppers. At room temperature, the changeover could be either complete or partial, depending on the solvent used. Photoinduced electron transfer from one of the Zn(II) porphyrins to the Au(III) porphyrin of the macrocycle was evidenced in the case of the free rotaxane and its Cu(I) complex, Zn2Cu+Au+. In the former case, the photoinduced electron transfer process could be clearly resolved for an extended conformation that is characterized by the Zn(II) porphyrins pointing far from the Au(III) porphyrin electron acceptor, and accounting for 30% of the total in acetonitrile at room temperature. In both Zn2Cu+Au+ and Zn-2-Au+ rotaxanes, the charge-separated state, in which the Zn(II) porphyrin is a cation radical and the Au(III) porphyrin a neutral radical, was generated at a rate of 5 x 10(9) s(-1) and disappeared at a rate of 2 x 10(8) s(-1). In the case of Zn2Cu+Au+, the primary step is very Likely energy transfer from the Zn(II) porphyrin singlet excited state to the MLCT state of the central Cu(I) complex, followed by an electron transfer from the excited Cu(I) unit to the Au(III) porphyrin and a successive charge shift from the Zn(ll) porphyrin to the oxidized Cu(Ll) complex. [2]-rotaxane Zn-2-Au+, in which no bond pathway can be identified between the donor and the, acceptor, is a typical case of electron transfer involving molecular fragments connected by mechanical bonds.

  DOI：

  10.1021/ja002018f
• 作为产物：
  描述：

  在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 以>99的产率得到gold(III) 5,10-di(p-hydroxyphenyl)-15,20-di(3,5-di-tert-butylphenyl)porphyrinate hexafluorophosphate
  参考文献：
  名称：

  Multiporphyrinic Rotaxanes: Control of Intramolecular Electron Transfer Rate by Steering the Mutual Arrangement of the Chromophores

  摘要：

  A [2]-rotaxane Zn-2-Au+ made from a dumbbell component ended by Zn(II) porphyrin stoppers and a ring component incorporating a Au(III) porphyrin has been assembled in 13% yield using the transition metal templating route. H-1 NMR studies show that its:conformation in solution is very different from those of its complexes with Cu+, Ag+, and Li+. In particular, removal of the templating metal resulted in a changeover of the molecule, the threaded macrocycle undergoing a pirouetting motion placing the Au(III) porphyrin in the deft formed by the two Zn(II) porphyrin stoppers. At room temperature, the changeover could be either complete or partial, depending on the solvent used. Photoinduced electron transfer from one of the Zn(II) porphyrins to the Au(III) porphyrin of the macrocycle was evidenced in the case of the free rotaxane and its Cu(I) complex, Zn2Cu+Au+. In the former case, the photoinduced electron transfer process could be clearly resolved for an extended conformation that is characterized by the Zn(II) porphyrins pointing far from the Au(III) porphyrin electron acceptor, and accounting for 30% of the total in acetonitrile at room temperature. In both Zn2Cu+Au+ and Zn-2-Au+ rotaxanes, the charge-separated state, in which the Zn(II) porphyrin is a cation radical and the Au(III) porphyrin a neutral radical, was generated at a rate of 5 x 10(9) s(-1) and disappeared at a rate of 2 x 10(8) s(-1). In the case of Zn2Cu+Au+, the primary step is very Likely energy transfer from the Zn(II) porphyrin singlet excited state to the MLCT state of the central Cu(I) complex, followed by an electron transfer from the excited Cu(I) unit to the Au(III) porphyrin and a successive charge shift from the Zn(ll) porphyrin to the oxidized Cu(Ll) complex. [2]-rotaxane Zn-2-Au+, in which no bond pathway can be identified between the donor and the, acceptor, is a typical case of electron transfer involving molecular fragments connected by mechanical bonds.

  DOI：

  10.1021/ja002018f

文献信息

• A [2]-catenane whose rings incorporate two differently metallated porphyrins
  作者：Myriam Linke、Norifumi Fujita、Jean-Claude Chambron、Vale´rie Heitz、Jean-Pierre Sauvage

  DOI：10.1039/b100275a

  日期：——

  A [2]-catenane made with Zn(II) and Au(III) porphyrin-incorporating marcrocycles has been synthesized using the transition metal templated technique, starting from either preformed Au or Zn porphyrin-containing macrocycles. The highest yield (11.5%) was obtained in the latter case. Removal of the copper(I) template metal afforded the free [2]-catenane, whose 1H-NMR properties differ dramatically from those of the parent Cu(I) complex, suggesting a changeover in the molecular structure upon demetallation.

  使用过渡合成了由 Zn(II) 和 Au(III) 卟啉结合大环制成的 [2]-链烯 金属模板技术，从预先形成的含金或锌卟啉大环化合物开始。最高的 在后一种情况下获得了产率（11.5%）。去除铜(I)模板金属得到游离的[2]-链烯， 其 1H-NMR 性质与 母体 Cu(I) 络合物，表明脱金属后分子结构发生了变化。