N-Porphyrinylamino and -amido Compounds by Addition of an Amino or Amido Nitrogen to a Porphyrin Meso Position
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- 作者：K. Jayaraj ; A. Gold ; L. M. Ball ; and P. S. White
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：August 7, 2000
- 年：2000
- 卷：39
- 期：16
- 页码：3652 - 3664
- 全文大小：258K
- 年卷期：v.39,no.16(August 7, 2000)
- ISSN：1520-510X
文摘
This report describes the synthesis and characterization of a series of octaethylporphyrin derivatives in which theporphyrin 
-network is connected to phenyl, 3-fluoranthenyl, or 1-pyrenyl aromatic systems through a mesoamino or amido nitrogen. Metal-free bases and zinc(II) and iron(III) complexes have been obtained. Thesecompounds represent the first examples of linkages between porphyrins and extended -networks through a nitrogenatom directly attached to a porphyrin meso position. 1H NMR studies of the metal-free bases and zinc complexesshowed that in the amido-linked adducts, the plane containing the aryl substituent was oriented perpendicular tothe plane of the porphyrin. Linkage through the secondary amino nitrogen, however, allowed the aryl plane torotate toward coplanarity with the porphyrin plane, resulting in conjugation of the highest occupied aryl andporphyrin molecular orbitals through the nitrogen lone pair. In developing routes to the amino-linked compounds,the facile formation of fused azaaryl chlorins via an oxidative intramolecular cycloaddition was observed. Anaryl carbon ortho to the meso linkage attacked the 
-carbon of an adjacent pyrrole ring, accompanied by 1,2-migration of a pyrrole -ethyl substituent and a two-electron oxidation of the initially formed macrocycle. Theresulting structures are analogous to benzochlorins. The electronic spectra of the metal-free bases are characterizedby intense, long-wavelength bands in the visible region. Molecular structures of the chloroferric complexes of theazabenzofluorantheno- and azabenzpyrenoporphyrin macrocycles (derived from fusion of the fluoranthenyl andpyrenyl substituents, respectively) were obtained by X-ray diffraction. The porphyrin moiety in the azabenzofluoranthenoporphyrin adopted a gable structure, with a 22
fold along a diagonal including the pyrrole-ring C4and C16 
-carbons. By contrast, the azabenzpyrenoporphyrin was virtually planar.
-network is connected to phenyl, 3-fluoranthenyl, or 1-pyrenyl aromatic systems through a mesoamino or amido nitrogen. Metal-free bases and zinc(II) and iron(III) complexes have been obtained. Thesecompounds represent the first examples of linkages between porphyrins and extended -networks through a nitrogenatom directly attached to a porphyrin meso position. 1H NMR studies of the metal-free bases and zinc complexesshowed that in the amido-linked adducts, the plane containing the aryl substituent was oriented perpendicular tothe plane of the porphyrin. Linkage through the secondary amino nitrogen, however, allowed the aryl plane torotate toward coplanarity with the porphyrin plane, resulting in conjugation of the highest occupied aryl andporphyrin molecular orbitals through the nitrogen lone pair. In developing routes to the amino-linked compounds,the facile formation of fused azaaryl chlorins via an oxidative intramolecular cycloaddition was observed. Anaryl carbon ortho to the meso linkage attacked the -carbon of an adjacent pyrrole ring, accompanied by 1,2-migration of a pyrrole -ethyl substituent and a two-electron oxidation of the initially formed macrocycle. Theresulting structures are analogous to benzochlorins. The electronic spectra of the metal-free bases are characterizedby intense, long-wavelength bands in the visible region. Molecular structures of the chloroferric complexes of theazabenzofluorantheno- and azabenzpyrenoporphyrin macrocycles (derived from fusion of the fluoranthenyl andpyrenyl substituents, respectively) were obtained by X-ray diffraction. The porphyrin moiety in the azabenzofluoranthenoporphyrin adopted a gable structure, with a 22 fold along a diagonal including the pyrrole-ring C4and C16 -carbons. By contrast, the azabenzpyrenoporphyrin was virtually planar.