5,5'-(ethane-1,2-diyl)bis(2,3,7,8,12,13,17,18-octaethylporphyrinatozinc) | 92995-45-4

• 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: 5,5'-(ethane-1,2-diyl)bis(2,3,7,8,12,13,17,18-octaethylporphyrinatozinc)
• 英文别名: 1,2-bis(5[zinc(II) octaethylporphyrinyl])ethane；(μ-ethane)bis(zinc octaethylporphyrin)；(5,5'-ethylenbis(octaethylporphyrinato))Zn2
• CAS: 92995-45-4
• 化学式: C₇₄H₉₀N₈Zn₂
• 分子量: 1222.36
• InChiKey: FEFYYVDUZMGZPC-IUKRXSGUSA-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

安全信息

• 危险等级：
  6.1

反应信息

• 作为反应物：
  描述：

  5,5'-(ethane-1,2-diyl)bis(2,3,7,8,12,13,17,18-octaethylporphyrinatozinc) 、 (R)-(-)-仲丁胺 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  锌卟啉的超分子手性：平衡、结合特性和热力学

  摘要：

  通过与手性单胺和一元醇客体相互作用，研究了非手性宿主分子 Syn（面对面构象）乙烷桥连双（锌卟啉）中超分子手性诱导的络合机制、结合特性和热力学参数UV-vis、CD、(1)H NMR 和 ESI MS 技术。发现手性形成过程包括三个主要的平衡步骤：第一次客体连接到宿主的锌卟啉亚基 (K(1))，顺式到反构象转换 (K(S))，以及通过第二个进一步连接客分子到剩余的无配体锌卟啉亚基 (K(2))，从而形成具有超分子手性的最终双连接物种。这种平衡模型的有效性通过计算和实验观察到的双连接物种的光谱参数之间的极好匹配得到证实。对于所有研究的超分子系统，无论手性配体的结构如何，第二次连接都以合作方式进行，因为 K(2) > K(1)。结合特性高度依赖于官能团的性质（胺是比醇更强的结合剂）和手性客体的结构（伯胺和脂肪胺的总结合常数值分别大于仲胺和芳香胺的总结合常数值） .

  DOI：

  10.1021/ja0172520
• 作为产物：
  描述：

  5,5'-(ethane-1,2-diyl)bis<2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin> 在 zinc diacetate 作用下， 生成 5,5'-(ethane-1,2-diyl)bis(2,3,7,8,12,13,17,18-octaethylporphyrinatozinc)
  参考文献：
  名称：

  Syn–anti conformational switching: Synthesis and X-ray structures of tweezer and anti form in a zinc porphyrin dimer induced by axial ligands

  摘要：

  Stepwise addition of 1,2-diaminobenzene to a Zn-1,2-bis(meso-octaethylporphyrinyl)ethane produces both tweezer and anti-form of the complex depending on the concentration of the axial ligand which exhibit two major equilibrium steps (with two step-wise binding constants): first, guest ligation leading to the formation of 1:1 host-guest tweezer structure (K-1) and, second, guest molecule ligation (K-2) forming 1:2 host-guest anti species and the corresponding binding constants are 1.82 x 10(3) M-1 and 1.34 x 10(2) M-1, respectively. However, when guest like 1,4-diaminobenzene and 4-CN-pyridine are used, the ligand geometry prevents its entry into interporphyrin cavity to form a tweezer structure, thus producing only the 1:2 anti complex. Single crystal X-ray structures of both tweezer and anti form produced in a single Zn-bisporphyrin are reported here for the first time. The nonbonding Zn center dot center dot center dot Zn distance within a molecule is 5.55 and 10.01 angstrom in tweezer and anti form, respectively. Although the average Zn-N (por) distances are comparable for both the forms, the Zn-N (1,2-diaminobenzene/4-CN-pyridine) distances and the displacement of Zn from the mean porphyrin planes are larger in tweezer compared to anti conformation. (C) 2011 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.01.101

文献信息

• Interactions of Two Porphyrin Rings: Metal-Induced Structural Change of 5,5′-Ethylenebis(porphyrin)
  作者：Ken-ichi Sugiura、Gelii Ponomarev、Satoshi Okubo、Akio Tajiri、Yoshiteru Sakata

  DOI：10.1246/bcsj.70.1115

  日期：1997.5

  5,5′-Ethylenebis(octaethylporphyrin) 1 and its metallocomplexes with various combination of metals (Zn, Cu, and Ni) 2—10 were prepared. On the basis of 1H and 13C NMR as well as MCD spectra, it was concluded that interactions between the two intramolecular porphyrins become attractive when at least one of the two rings is converted to zinc porphyrin. The phenomenon was explained by dipole–dipole interaction arising from the large polarization in Zn complexes.

  5,5′-乙烯双（八乙基紫杉烷）1及其与各种金属（锌、铜和镍）形成的金属复合物2—10被制备。基于1H和13C NMR谱以及MCD谱，得出结论：当至少有一个环转化为锌紫杉烷时，两个分子内紫杉烷之间的相互作用变得具有吸引力。这个现象是通过锌复合物中产生的大极化引起的偶极-偶极相互作用进行解释的。
• Remarkable Stability and Enhanced Optical Activity of a Chiral Supramolecular Bis-porphyrin Tweezer in Both Solution and Solid State
  作者：Victor V. Borovkov、Juha M. Lintuluoto、Makiko Sugiura、Yoshihisa Inoue、Reiko Kuroda

  DOI：10.1021/ja026884z

  日期：2002.9.1

  (face-to-face) conformer of the ethane-bridged bis(zinc octaethylporphyrin) with the enantiopure 1,2-diaminocyclohexane results in the exclusive formation of a supramolecular chiral tweezer. This 1:1 host-guest complex exhibits remarkable stability in both solution (even upon photoexcitation) and solid-state phases, with a high degree of optical activity arising from the two-point interaction mode and

  乙烷桥连双（八乙基卟啉锌）的非手性顺式（面对面）构象异构体与对映体纯 1,2-二氨基环己烷的相互作用导致超分子手性镊子的独家形成。这种 1:1 的主客体复合物在溶液（即使在光激发时）和固态相中都表现出显着的稳定性，并且由于两点相互作用模式和最佳空间几何形状而具有高度的光学活性。
• Phase-Sensitive Supramolecular Chirogenesis in Bisporphyrin Systems
  作者：Victor V. Borovkov、Takunori Harada、Yoshihisa Inoue、Reiko Kuroda

  DOI：10.1002/1521-3773(20020415)41:8<1378::aid-anie1378>3.0.co;2-l

  日期：2002.4.15
• Rationalization of Supramolecular Chirality in a Bisporphyrin System
  作者：Victor V. Borovkov、Isao Fujii、Atsuya Muranaka、Guy A. Hembury、Takeyuki Tanaka、Arnout Ceulemans、Nagao Kobayashi、Yoshihisa Inoue

  DOI：10.1002/anie.200460965

  日期：2004.10.18