Syntheses and properties of gallium, silicon, germanium, and tin octaethylporphyrins and etioporphyrins

Syntheses, physical properties, and chemical properties of new gallium, silicon, germanium, and tin octaethylporphyrins and etioporphyrins are described. Also described are syntheses of a novel class of silicon and germanium octaethylporphyrin-phthalocyanine compounds.; Among the octaethylporphyrins and etioporphyrins characterized are monomeric species with halo, hydroxy, alkoxy, and siloxy ligands. Members of this group are typically quite stable. They are soluble in common organic solvents and generally can be chromatographed. These compounds yield infrared and electronic spectra with bands in expected positions and NMR spectra with resonances in positions that indicate the presence of large ring-current effects.; Ga(OEP)F and Ga(Etio)F have also been characterized. While Ga(OEP)F is monomeric under ordinary conditions, Ga(Etio)F can be monomeric or polymeric depending on the preparation method. The polymeric forms of Ga(Etio)F isolated have a ring-ring spacing of {dollar}sim{dollar}3.86 A. Preliminary data indicate that these polymeric forms are readily doped by iodine and are moderately good conductors when doped.; In addition, silicon and germanium octaethylporphyrin and etioporphyrin oligomers have been characterized. These oligomers have {dollar}mu{dollar}-oxo bridges and cofacial rings. They are stable and are soluble in common organic solvents. They give electronic spectra with Soret bands that have the expected blue-shifts and NMR spectra that show the presence of large ring-current effects.; Finally silicon and germanium two-ring {dollar}mu{dollar}-oxo bridged octaethylporphyrin-phthalocyanine compounds have been characterized. These compounds also have cofacially arranged rings. They are soluble in common organic solvents, yield infrared spectra with M-O-M bands, electronic spectra with unusual bands, and NMR spectra with resonances in positions that suggest the presence of large ring-current effects. The unusual bands in the electronic spectra of these compounds indicate that the close cofacial arrangement of the two types of rings in them leads to molecular orbitals that differ substantially from those of the independent rings.