| 199394-10-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 199394-10-0
• 化学式: C₄₆H₁₃F₁₅N₄Zn
• 分子量: 972.002
• InChiKey: KLKGERRNVPDHOW-PHDQBPJISA-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

• 作为反应物：
  描述：

  5-(p-iodophenyl)-10,15,20-tris (pentafluorophenyl) porphyrin 、 在 Pd₂(dba)3AsPh₃ 作用下， 以 三乙胺 、 甲苯 为溶剂， 以81%的产率得到
  参考文献：
  名称：

  Effects of Orbital Ordering on Electronic Communication in Multiporphyrin Arrays

  摘要：

  The rational design of molecular photonic devices requires a thorough understanding of all factors affecting electronic communication among the various constituents. To explore how electronic factors mediate both excited- and ground-state electronic communication in multiporphyrin arrays, we have conducted a detailed static spectroscopic (absorption, fluorescence, resonance Raman, electron paramagnetic resonance), time-resolved spectroscopic (absorption, fluorescence), and electrochemical (cyclic and square-wave voltammetry, coulometry) study of tetraarylporphyrin dimers, The complexes investigated include both zinc-free base (ZnFb) and bis-Zn dimers in which the porphyrin constituents are linked via diphenylethyne groups at the meso positions. Comparison of dimeric arrays containing pentafluorophenyl groups at all nonlinking meso positions (F(30)ZnFbU and F30Zn2U) with nonfluorinated analogs (ZnFbU and Zn2U) directly probes the effects of electronic factors on intradimer communication. The major findings of the study are as follows: (1) Energy transfer from the photoexcited Zn porphyrin to the Fb porphyrin is the predominant excited-state reaction in F(30)ZnFbU, as is also the case for ZnFbU. Energy transfer primarily proceeds via a through-bond process mediated by the diarylethyne linker. Remarkably, the energy-transfer rate is 10 times slower in F(30)ZnFbU ((240 ps)(-1)) than in ZnFbU ((24 ps)(-1)), despite the fact that each has the same diphenylethyne linker. The attenuated energy-transfer rate in the former dimer is attributed to reduced Q-excited-state electronic coupling between the Zn and Fb porphyrins. (2) The rate of hole/electron hopping in the monooxidized bis-Zn complex, [F30Zn2U](+), is similar to 10-fold slower than that for [Zn2U](+). The slower hole/electron hopping rate in the former dimer reflects strongly attenuated ground-state electronic coupling. The large attenuation in excited-and groundstate electronic communication observed for the fluorine-containing dimers is attributed to a diminution in the electron-exchange matrix elements that stems from stabilization of the a(2u) porphyrin orbital combined with changes in the electron-density distribution in this orbital. Stabilization of the porphyrin a(2u) orbital results in a switch in the HOMO from at, in ZnFbU to a(1u) in F(30)ZnFbU. This orbital reversal diminishes the electron density at the peripheral positions where the linker is appended. Collectively, our studies clarify the origin of the different energy-transfer rates observed among various multiporphyrin arrays and exemplify the interconnected critical roles of a(1u)/a(2u), orbital ordering and linker position in the design of efficient molecular photonic devices.

  DOI：

  10.1021/ja971678q

文献信息

• Synthesis of Thiol-Derivatized Porphyrin Dimers and Trimers for Studies of Architectural Effects on Multibit Information Storage
  作者：Christian Clausen、Daniel T. Gryko、Rajeev B. Dabke、Narasaiah Dontha、David F. Bocian、Werner G. Kuhr、Jonathan S. Lindsey

  DOI：10.1021/jo000488m

  日期：2000.11.1

  trimers incorporates a trans-substituted porphyrin (central) bearing two S-acetylthio groups and two diphenylethyne-linked porphyrins (wings) in a trans geometry. The central porphyrin and the wing porphyrins bear distinct substituents and central metals, thereby affording different oxidation potentials. The S-acetylthio groups provide a means for attachment of the arrays to an electroactive surface. The

  我们目前的合理设计和包含硫醇衍生的接头的多卟啉阵列的合成，以用于多位分子信息存储。卟啉二聚体和三聚体是通过Pd介导的碘取代和乙炔基取代的卟啉结构单元的偶联以5-51％的产率合成的。每个卟啉二聚体带有一个S-乙酰硫基。三聚体的结构包含反式几何结构中带有两个S-乙酰硫基和两个二苯乙炔连接的卟啉（翼）的反式卟啉（中央）。中心卟啉和侧卟啉带有不同的取代基和中心金属，从而提供不同的氧化电位。S-乙酰硫基提供了将阵列连接至电活性表面的手段。二聚体设计用于在电活性表面上垂直定向，而三聚体设计用于中心卟啉的水平定向。总共合成了七个不同的阵列。每个阵列通过原位切割S-乙酰基保护基团在金上形成自组装单层（SAM）。每个阵列的SAM具有电化学稳定性，并表现出多个可逆的氧化波。但是，一般而言，三聚体阵列似乎形成了更高度有序的单分子层，这些单分子层表现出更清晰，定义更好的氧化还原特征。每个阵列的SAM具有电化学稳定