Zn(II)(αalphaαalpha.)-5,10,15,20-tetrakis(2-(4-fluorophenylurea)phenyl)porphyrin | 197440-54-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: Zn(II)(αalphaαalpha.)-5,10,15,20-tetrakis(2-(4-fluorophenylurea)phenyl)porphyrin
• CAS: 197440-54-3
• 化学式: C₇₂H₄₈F₄N₁₂O₄Zn
• 分子量: 1286.63
• InChiKey: POSLDUOZGMWFGA-GIZPQBOTSA-L

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

• 作为产物：
  描述：

  (α,α,α,α)-5,10,15,20-tetrakis(2-(4-fluorophenylurea)phenyl)porphyrin 、 zinc(II) acetate dihydrate 以 甲醇 、 二氯甲烷 为溶剂， 以95%的产率得到Zn(II)(αalphaαalpha.)-5,10,15,20-tetrakis(2-(4-fluorophenylurea)phenyl)porphyrin
  参考文献：
  名称：

  (cis)-5,10,15,20-Tetrakis[2-(arylurea)phenyl]porphyrins: novel neutral ligands for remarkably selective and exceptionally strong chloride anion complexation in (CD3)2SO

  摘要：

  添加了尿素的游离基卟啉 2-4 与 (CD 3 ) 2 SO 中的球形 Cl - 结合力很强（K > 10 5 dm 3 mol - 1），并表现出明显的结合选择性，因为它们与 Cl - 的络合程度（10 3 -10 2 :1）远高于与三方 NO 3 - 和四方 H 2 PO 4 - 阴离子的络合程度。

  DOI：

  10.1039/a702389h

文献信息

• Neutral Ligands for Selective Chloride Anion Complexation:  (α,α,α,α)-5,10,15,20-Tetrakis(2-(arylurea)phenyl)porphyrins
  作者：Raymond C. Jagessar、Maoyu Shang、W. Robert Scheidt、Dennis H. Burns

  DOI：10.1021/ja982052i

  日期：1998.11.1

  A series of neutral, urea-appended, free-base porphyrins and their Zn(II) complexes have been synthesized and characterized. The (alpha,alpha,alpha,alpha)-5,10,15,20-tetrakis(2-(arylurea)phenyl)porphyrins bind strongly (K (M-1) > 10(3)-10(5)) to chloride anion in DMSO-d(6) and also in the more competitive solvent system DMSO-d(6)/D2O (88:12, v/v) and bromide anion in DMSO-d(6), as revealed by H-1 NMR titration studies. The porphyrin derivatives exhibited significant binding selectivity since they complexed with the spherical Cl- and Br- to a much greater extent than with the tetrahedral H2PO4- and HSO4- and the trigonal NO3- anions in DMSO-d(6). Indeed, the selectivity trend Cl- > Br- much greater than H2PO4- > HSO4- > NO3- is novel for any neutral urea-anion binding system. On the other hand, the corresponding metalloporphyrins exhibited a decrease in binding strength and selectivity in DMSO-d(6). The stoichiometry of binding for the anions and porphyrins was determined to be 1:1. The enthalpy of complexation was determined to be highly favorable and the entropy of complexation determined to be unfavorable from a variable-temperature H-1 NMR experiment with a 1:1 tetrabutylammonium bromide/porphyrin complex. X-ray crystallography revealed (alpha,alpha,alpha,alpha)-5,10,15,20-tetrakis(2-(4-chlorophenylurea)phenyl)porphyrin to be the first coordination complex of an anion (chloride and bromide) bound by a neutral free-base porphyrin. The binding motif consisted of the halide, buried deep within the porphyrin pocket, bound by two adjacent urea functional groups via four hydrogen bonds, with the two remaining urea functional groups involved in hydrogen bonding to solvent molecules. The crystal structure of the tetrabutylammonium halide-porphyrin complex showed additional Coulombic interaction between the electron-poor sulfur of a pocket-bound, hydrogen-bonded DMSO and halide anion.