(I) PREPARATION AND PROPERTIES OF SILICON HEMIPORPHYRAZINES. (II) STRATEGIES TO SIMPLIFY THE ROUTE TO PHTHALOCYANINES WITH BETA, BETA'-FUSED LINEARLY ANNELLATED POLYCYCLIC AROMATIC RING

Silicon hemiporphyrazines (Si(hp)Cl(,2), Si(hp)(OH)(,2), and (Si(hp)O)(,n)) have been prepared by reaction of SiCl(,4) with the free base hpH(,2). Properties (IR, UV-vis, solid state ('13)C NMR) of silicon hemiporphyrazines do not appear to differ appreciably from those of the analogous germanium compounds. X-ray powder diffraction suggests that Si(hp)(OH)(,2), (Si(hp)O)(,n), and (Ge(hp)O)(,n) are isostructural. Analysis of the powder patterns further suggests that the polymeric systems are interleaved. Tritium labeling end group analysis indicates the degrees of polymerization to be: (Si(hp)O)(,n), n (DBLTURN) 25; (Ge(hp)O)(,n), n (DBLTURN) 60. Attempted partial oxidation of the polymers with iodine appears to result in metal oxygen bond cleavage. Chapter II reports on a general procedure to make 2,3-dicyano-linearly annellated polycyclic aromatics (up to naphthacene) with the subsequent cyclization to phthalocyanines in mind. Thus, reaction of phthaldehyde, 2,3-naphthalenedicarboxaldehyde, or 2,3-anthracenedicarboxaldehyde with succinonitrile in the presence of NaOCH(,3) produces (I) 2,3-naphthalenedinitrile (46%), (II) 2,3-anthracenedinitrile (34%), or (III) 2,3-naphthacenedinitrile (60%), respectively. Reaction of (III) with sulfure produces a very dark green compound which--upon partial oxidation with iodine--has a conductivity of 10('-3)-10('-4) ((OMEGA)cm)('-1) (300(DEGREES)K). Appendix B reports on the preparation of copper anthraquinocyanine. ESR, IR, conductivity, and photoconductivity data are reported. Appendix C reports on the preparation of elastomeric ((Si(Pc)(OSi(Me)(,2)O)(,13-16))(,n)) and plastic ((Si(Pc)(OSi(Ph)(,2)O)(,13-16))(,n)) silicone phthalocyanines.