5,5'-(ethane-1,2-diyl)bis<2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin> | 64932-94-1

• 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-octaethyl-21H,23H-porphyrin>
• 英文别名: 5,5'-(ethane-1,2-diyl)bis[2,3,7,8,12,17,18-octaethyl-21H,23H-porphyrin]；1,2-bis(meso-octaethylporphyrinyl)ethane；1,2-di(octaethyl-5-porphyrinyl)ethane；5,5'-ethylenebis(octaethylporphyrin)；1,2-di(meso-octaethylporphyrinyl)ethane
• CAS: 64932-94-1
• 化学式: C₇₄H₉₄N₈
• 分子量: 1095.61
• InChiKey: LPFFAAZFZRSASJ-AFEBAAMMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.15
• 重原子数：
  82.0
• 可旋转键数：
  19.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  114.72
• 氢给体数：
  4.0
• 氢受体数：
  4.0

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-octaethyl-21H,23H-porphyrin> 在 copper (I) acetate 作用下， 以 氯仿 为溶剂， 反应 0.17h， 以93%的产率得到
  参考文献：
  名称：

  Interactions of Two Porphyrin Rings: Metal-Induced Structural Change of 5,5′-Ethylenebis(porphyrin)

  摘要：

  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。

  DOI：

  10.1246/bcsj.70.1115
• 作为产物：
  描述：

  在 硫酸 、 三氟乙酸 作用下， 生成 5,5'-(ethane-1,2-diyl)bis<2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin>
  参考文献：
  名称：

  卟啉。23.乙双卟啉的合成与性质

  摘要：

  DOI：

  10.1007/bf00475323

文献信息

• Synthesis and Characterization of<i>anti</i>-bisFe(III) Porphyrins,<i>syn</i>-bisFe(III)-μ-oxo Porphyrin, and<i>syn</i>-bisFe(III)-μ-oxo Porphyrin Cation Radical
  作者：Sudip Kumar Ghosh、Ranjan Patra、Sankar Prasad Rath

  DOI：10.1021/ic100002c

  日期：2010.4.5

  condition using aerial O2. Electrochemical data reveals that bis Fe(III)-μ-oxo porphyrin undergoes four one electron oxidations and one electron reduction. However, oxidations become easier in syn Fe(III)-μ-oxo dimer rather than the anti-form of the molecule (with axial ligand X). The presence of two porphyrin macrocycles within a short distance in the syn form makes the porphyrin core highly nonplanar

  据报道，由高柔性乙烷连接基桥接的BisFe（III）卟啉，其中双卟啉平台“打开”和“闭合”其结合口袋，导致在单个分子框架中具有非常高的垂直柔性的简便的顺-反构象转换。利用轴向配体X（X：Cl，Br，I，ClO 4），分子的反形式被稳定。据报道抗双高氯酸盐铁（III）卟啉的X射线结构，并且发现该分子在自然界中是高自旋的。与之形成鲜明对比的是，所有其他以ClO 4为轴向配体的Fe（III）卟啉均处于中间或混合自旋状态。非常强的Fe-OClO 3键和相对弱的Fe-N（p）键负责分子的高自旋性质。经碱处理后，生成了双Fe（III）-μ-氧代卟啉，其中Fe-O-Fe单元显着弯曲（成147.9（1）°角），并且分子中的两个卟啉环如此紧密，以至于来自每个卟啉大环的至少六个碳原子被驱动成基本上比范德华接触距离更近。当操纵该溶液中，轻便的酸度/碱度顺-反构象切换发生，这也是本质上是可逆的。该络合物在温和条件下使用空中O
• Experimental and Theoretical Investigation of a Series of Novel Dimanganese(III) μ-Hydroxo Bisporphyrins: Magneto–Structural Correlation and Effect of Metal Spin on Porphyrin Core Deformation
  作者：Debangsu Sil、Susovan Bhowmik、Firoz Shah Tuglak Khan、Sankar Prasad Rath

  DOI：10.1021/acs.inorgchem.5b02226

  日期：2016.4.4

  The synthesis, structure, and properties of a new family of five ethane-bridged dimanganese(III) μ-hydroxo bisporphyrins with the same core structure but different counteranions are reported here. Additions of 10% Brønsted acids such as HI, HBF4, HSbF6, HPF6, and HClO4 to a dichloromethane solution of the dichloro dimanganese(III) bisporphyrin produces complexes having a remarkably bent μ-hydroxo group

  本文报道了一个新的五族乙烷桥联的二锰（III）μ-羟基双卟啉新家族的合成，结构和性质，该结构具有相同的核心结构但具有不同的抗衡阴离子。10％布朗斯台德的添加酸如HI，HBF 4，HSbF 6，HPF 6，和高氯酸4到二氯二锰（III）的二氯甲烷溶液bisporphyrin产生具有显着的弯曲μ-羟基与I复合3 -，BF 4 –，SbF 6 –，PF 6 –和ClO 4 –分别作为抗衡阴离子。已经确定了所有配合物的X射线结构，揭示了在配合物中存在两个等效的高自旋锰（III）中心，卟啉环同样变形，与二价铁（III）μ形成鲜明对比-羟基双卟啉类似物。1 H NMR光谱显示了高度屏蔽的介观共振，这与二铁（III）类似物的情况不同，后者的介观共振被高度屏蔽。可变温度的磁数据经过最小二乘拟合，从而通过两个零场分裂Mn（III）中心之间的羟基桥提供了适度的反铁磁耦合，耦合常数为（J）的值范围从−29.5到−38
• Syn–anti conformational switching in an ethane-bridged Co(<scp>ii</scp>)bisporphyrin induced by external stimuli: effects of inter-macrocyclic interactions, axial ligation and chemical and electrochemical oxidations
  作者：Soumyajit Dey、Sankar Prasad Rath

  DOI：10.1039/c3dt52784k

  日期：——

  The syn–anti conformational switching has been demonstrated in the ethane-bridged dicobalt(II)bisporphyrin which is present in the syn-form only. The addition of either perylene or axial ligands to CoII(bisporphyrin) completely transforms the syn form into the anti because of strong π–π interaction and axial coordination, respectively. The complex undergoes four 1e-oxidations in CH2Cl2 which are indicative of strong through space interactions between the two cofacial Co-porphyrins at 295 K. The first oxidation is a metal centered one and occurs at a potential much lower than that of the monomeric analog. However, the second oxidation, which is again metal centered, was at a significantly higher potential. The large difference between the first two oxidations, as observed here, is due to much stronger inter-porphyrin interactions. The step-wise oxidations have been performed both chemically and electro-chemically while the progress of the reactions was monitored by UV-visible and 1H NMR spectroscopy. After 1e-oxidation, a very broad 1H NMR signal results with increased difference between two meso resonances, which indicates that the two macrocycles are in the syn-form with lesser interplanar separation as also observed by DFT. However, 2e-oxidation results in the stabilization of the anti form. The addition of axial ligands to CoII(bisporphyrin) also completely transforms the syn form into the anti form. While additions of THF and I2/I− both result in the formation of five-coordinate complexes, Co(II) is oxidized to Co(III) in the case of the latter. However, additions of 1-methylimidazole, pyridine and pyrazine as axial ligands result in the formation of a six-coordinate complex in which Co(II) is spontaneously oxidized to Co(III) in air.

  乙烷桥接的二钴(II)双卟啉仅以同位形式存在，这种同反构象转换在二钴(II)双卟啉中得到了证实。在 CoII（双卟啉）中加入过烯配体或轴向配体后，由于ÏâÏ相互作用和轴向配位作用分别很强，因此能将同位形式完全转变为反位形式。该复合物在 CH2Cl2 中发生了四次 1e- 氧化反应，这表明在 295 K 的温度下，两个共面卟啉之间存在强烈的空间相互作用。然而，第二次氧化也是以金属为中心的氧化，其电位明显更高。这里观察到的前两次氧化之间的巨大差异，是由于卟啉之间的相互作用要强得多。分步氧化是通过化学和电化学方法进行的，同时通过紫外可见光谱和 1H NMR 光谱监测反应的进展。1e 氧化后，会产生非常宽的 1H NMR 信号，两个中位共振之间的差异增大，这表明两个大环处于合成形式，平面间的分离较小，DFT 也观察到了这一点。然而，2e-氧化会导致反式的稳定。向 CoII（双卟啉）中添加轴向配体也会使同向形式完全转变为反向形式。加入四氢呋喃和 I2/Iâ 都会形成五配位络合物，但加入 I2/Iâ 时，Co(II)会被氧化成 Co(III)。然而，加入 1-甲基咪唑、吡啶和吡嗪作为轴配体会形成六配位络合物，其中的 Co(II) 会在空气中自发氧化成 Co(III)。
• Reagent for determining the absolute configuration of chiral compound and determination method
  申请人：Inoue Yoshihisa

  公开号：US20050107604A1

  公开（公告）日：2005-05-19

  The present invention relates to a reagent for determining the absolute configuration of a chiral compound containing as an active ingredient a metalloporphyrin dimer, wherein the metalloporphyrin dimer has an alkaline-earth metal ion as a central metal and has a carbon chain-crosslinked structure in which at least one of the two porphyrin rings has a substituent bulkier than methyl at at least one of the second carbon atoms from a carbon atom bonded to the crosslinking carbon chain along the outer periphery of the porphyrin ring and a method for determining the absolute configuration of an asymmetric carbon atom of the chiral compound using the reagent.

  本发明涉及一种试剂，用于确定手性化合物的绝对构型，所述手性化合物包含作为活性成分的金属卟啉二聚体，其中金属卟啉二聚体具有碱土金属离子作为中心金属，并且具有碳链交联结构，其中至少两个卟啉环中的至少一个卟啉环在外周沿交联碳链与一个碳原子键合的第二个碳原子处具有比甲基更大的取代基，以及使用该试剂确定手性化合物的不对称碳原子的绝对构型的方法。
• Silver(III)⋅⋅⋅Silver(III) Interactions that Stabilize the <i>syn</i> Form in a Porphyrin Dimer Upon Oxidation
  作者：Akhil Kumar Singh、Firoz Shah Tuglak Khan、Sankar Prasad Rath

  DOI：10.1002/anie.201705108

  日期：2017.7.17

  interaction between two AgII porphyrins, connected covalently through a highly flexible ethane bridge, in a metalloporphyrin dimer has been investigated upon stepwise oxidation. X‐ray structure determination of one and two‐electron oxidized complexes has clearly revealed only metal‐centered oxidation that results in short Ag−N (porphyrin) distance with large distortion in the porphyrin macrocycle. The 2e‐oxidized

  通过逐步氧化，已经研究了在金属卟啉二聚体中通过高度柔性的乙烷桥共价连接的两个Ag II卟啉之间的相互作用。X射线对一种和两种电子氧化的配合物的结构测定清楚地表明，仅以金属为中心的氧化会导致较短的Ag-N（卟啉）距离，并在卟啉大环中产生较大的畸变。以紧密的Ag的形式2E氧化复杂展品显著metallophilic相互作用III ⋅⋅⋅Ag III接触时带来了两个卟啉环更多共面与顺-conformation，否则稳定的抗-形式。在光致发光研究中，该相互作用还导致在77 K处的546 nm处出现强烈的发射峰。