Synthesis, lead lability and ring deformation of three 1,4,8,11,15,18,22,25-octasubstituted phthalocyaninato lead derivatives

Abstract

The syntheses and attempted syntheses of some non-peripherally (1,4,8,11,15,18,22,25) octasubstituted lead phthalocyanines from their corresponding metal-free derivatives are described. Some compounds exhibited lability of the lead ion during work-up to regenerate the starting material. The results of single crystal X-ray diffraction analyses of 1,4,8,11,15,18,22,25-octahexyl-, 1,4,8,11,15,18,22,25-octa-iso-pentyl- and 1,4,8,11,15,18,22,25-octahexylsulfanyl lead phthalocyanines are reported and cast some light on the greater stability of 1,4,8,11,15,18,22,25-octahexylsulfanyl lead phthalocyanine, in terms of ease of loss of the lead ion, over the other two substituted lead phthalocyanines studied. The phthalocyanine cores of all three derivatives adopt a saddle-shaped geometry rather than the saucer-shaped conformation exhibited by unsubstituted lead phthalocyanine. The saddle-shaped conformation would appear to offer a means of relieving steric interactions between the substituents on adjacent benzene rings. That steric interactions are a feature of these molecules is perhaps reflected in the different distortions of the saddle conformations. This is greatest for compound 1,4,8,11,15,18,22,25-octa-iso-pentyl lead phthalocyanine bearing the isopentyl groups, expected to introduce the most interactions, and least for compound 1,4,8,11,15,18,22,25-octahexylsulfanyl lead phthalocyanine where S atoms rather than methylene groups are adjacent to the benzene ring. The molecules of 1,4,8,11,15,18,22,25-octahexyl- and 1,4,8,11,15,18,22,25-octahexylsulfanyl lead phthalocyanine pack together in pairs with their nearest neighbouring molecule; their lead atoms, displaced from the core and directed towards each other. The presence of the S atoms in 1,4,8,11,15,18,22,25-octahexylsulfanyl lead phthalocyanine leads to close Pb … S contacts between the molecules. Attractive Pb … S interactions in this compound may also account for the larger displacement of the Pb from the mean-plane of the four coordinated nitrogen atoms at the centre of the phthalocyanine core than is found for 1,4,8,11,15,18,22,25-octahexyl- and 1,4,8,11,15,18,22,25-octa-iso-pentyl lead phthalocyanines. The molecular packing of 1,4,8,11,15,18,22,25-octa-iso-pentyl lead phthalocyanine is more complex because of the presence of tetrahydrofuran molecules (the solvent of recrystallisation) within the crystal, offering additional interactions with the Pb atoms.