[2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-(2,2'-[2''-(2'''-[2''''-(1''''',5'''''-naphthoxy)ethoxy]ethoxy)ethoxy]diphenyl)porphyrinato]zinc(II) | 157742-89-7

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: [2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-(2,2'-[2''-(2'''-[2''''-(1''''',5'''''-naphthoxy)ethoxy]ethoxy)ethoxy]diphenyl)porphyrinato]zinc(II)
• 英文别名: 2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-{1,5-naphthylenebis{{{{{(oxyethylene)oxy}ethylene}oxy}ethylene}phenyl}}porphyrinatozinc(II)
• CAS: 157742-89-7
• 化学式: C₆₆H₇₂N₄O₈Zn
• 分子量: 1114.71
• InChiKey: UTEGQZIRFPYPQN-KIDUYPIDSA-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：

  [2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-(2,2'-[2''-(2'''-[2''''-(1''''',5'''''-naphthoxy)ethoxy]ethoxy)ethoxy]diphenyl)porphyrinato]zinc(II) 、 2,7-di(prop-2-ynyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone 在 bis-triphenylphosphine-palladium(II) chloride 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以16%的产率得到[2]-([2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-[2,2'-(2''-[2'''-[2''''-(1''''',5'''''-naphthoxy)ethoxy]ethoxy]ethoxy)diphenyl]porphyrinato]zinc(II))(cyclobis(1,4,5,8-naphthalenetetracarboxylic diimide-hexa-2,4-diyne))catenane
  参考文献：
  名称：

  Neutral π-associated porphyrin [2]catenanes

  摘要：

  一系列中性含卟啉的链烷已经合成，由锌卟啉和含有四个或六个乙氧基单元的聚乙二醇链组成，并包含一个中心萘醌单元，与萘二酰亚胺大环相互连接。萘二酰亚胺前体单元与束缚卟啉的结合力较弱（Ka在8和0.02 M之间），但在卟啉存在的情况下，通过炔基萘二酰亚胺前体的格拉瑟偶联，获得了良好的链烷产量。通过质谱和详细的1H NMR研究确定了结构和溶液构象。对于较长的束缚卟啉，二酰亚胺大环以每秒420-450次的频率绕中心萘醌单元旋转，而在更紧密的束缚衍生物中，旋转实际上被阻止了。在两组链烷中发生的第二个动态过程被称为“偏航”，导致萘部分的不等价。紫外可见光谱表明链烷的两个成分之间存在电荷转移相互作用和电子通信。

  DOI：

  10.1039/b307383a

文献信息

• Thermodynamically self-assembling porphyrin-stoppered rotaxanes
  作者：Maxwell J. Gunter、Nick Bampos、Ken D. Johnstone、Jeremy K. M. Sanders

  DOI：10.1039/b006911f

  日期：——

  could be crystallised from solution and chromatographed at low temperatures; at higher temperatures only a mixture of the components separated on chromatography. 1H NMR revealed NOE correlations between all three components for the rotaxane, and exchange peaks for related free and complexed species. The temperature and concentration dependence of the equilibria were studied by NMR methods, and van't Hoff

  通过对组分和温度的明智选择，在热力学可逆性条件下组装了多种卟啉封端的轮烷。螺纹单元的混合物，包括中央萘二酰亚胺和末端吡啶（2a），环单元二萘酚-38-冠-10（1）和Zn II（3a），Ru II（CO）（3b）或Rh III I （3分），因为塞子显示出形成了假轮烷和卟啉塞住的轮烷的平衡混合物。完整的轮烷可以从溶液中结晶出来，并在低温下进行色谱分离。在更高的温度下，仅色谱分离了组分的混合物。1 H NMR揭示了轮烷的所有三个组分之间的NOE相关性，以及相关的游离和络合物种的交换峰。通过NMR方法研究了平衡的温度和浓度依赖性，Ru（CO）塞子系统的van't Hoff图可以估算ΔH °和ΔS °，-41.4 kJ mol -1和-95 JK -1摩尔-1分别和ķ一个在273K的790米之-1，上升到5.39×10 4中号-1在223 K.对于瓶塞准轮烷系统1 -图2a和1 -图2b中，- [R
• Self-Assembling Porphyrin [2]-Catenanes
  作者：Maxwell J. Gunter、David C. R. Hockless、Martin R. Johnston、Brian W. Skelton、Allan H. White

  DOI：10.1021/ja00090a029

  日期：1994.6

  Using the concepts of self-assembly developed for the construction of topologically complex molecules such as [2]-catenanes and rotaxanes, the syntheses of several prophyrin-catenanes are described. The successful insertion of the porphyrin subunit into [2]-catenanes has resulted from the adaptation of previously devised template-directed syntheses based primarily on pi-pi interactions and C-H...O and C-H...pi and hydrogen bonding. Several hydroquinol containing ether chains were successfully synthesized and subsequently strapped across a porphyrin ring; the X-ray crystal structures of two such molecules which vary in the length of the ether chain are reported. These strapped porphyrins were found to complex paraquat with a parallel orientation of the hydroquinol, paraquat, and porphyrin rings. The complexation of paraquat (K-a 1955 and 1640 M(-1), Delta G degrees = -4.5 and -4.4 kcal mol(-1) for 9 and 11, respectively) by these strapped porphyrins led to their subsequent inclusion, using template-directed self-assembly, into structures which represent the first examples of porphyrin-containing [2]-catenanes. The catenanes were subsequently characterized by FAB-MS and thoroughly examined using dynamic H-1 NMR. In the case of the hydroquinol-containing catenanes, a dynamic process was observed in solution in which the bipyridinium subunits of the tetracation were exchanged between ''inside'' and ''outside'' environments (rotation around the hydroquinol ring axis). The diethylene glycol containing catenanes 14 and 15 were observed to maintain an orientation of the tetracation in which the bipyridinium subunits are parallel to the porphyrin ring. The length of the ether strap in these catenanes influenced the rotation rates of the tetracation macrocycles (50 and 80 times per second for 14 and 15 and 2500 and 1500 times per second for 16 and 17, respectively) at ambient temperature. However, in air the catenanes, the overall orientation of the tetracation,with bipyridinium and porphyrin rings coparallel, is retained in solution. As an extension of the original concepts, an analogous strapped porphyrin containing a naphthoquinol moiety was synthesized and found to complex paraquat with K-a = 21 000 M(-1) and Delta G degrees = -5.9 kcal mol(-1). The general applicability of the template-directed synthetic procedure developed for porphyrin catenane synthesis was illustrated by the successful isolation of the naphthalene containing porphyrin [2]-catenane 23 in 45% yield. Tetracation exchange processes similar to those for the hydroquinol catenanes were observed, along with an additional process which was found to be the decomplexation/complexation of the naphthalene ring in what is termed an ''out, turn around, and in again'' process similar to that occurring in nonporphyrinic naphthalene [2]-catenanes.