  Herein, we present a series of isomerically pure, peripherically alkyl
substituted, soluble and low aggregating azaphthalocyanines as well as their
new, smaller hybrid homologues, the azasubphthalocyanines. The focus lies on
the effect of the systematically increasing number of aza building blocks [-N=]
replacing the non peripheral [-CH=] units and its influence on physical and
photophysical properties of these chromophores. The absolute and relative
HOMO-LUMO energies of azaphthalocyanines was analyzed using UV-Vis, CV and
compared to density functional theory calculations (B3LYP, TD-DFT). Crystals of
substituted subphthalocyanine, N2-Pc*H2 and N4-[Pc*Zn$\cdot$H2O] were obtained
out of DCM. For the synthesis of the valuable tetramethyltetraline
phthalocyanine building block a new highly efficient synthesis involving a
nearly quantitative CoII catalyzed aerobic autoxidation step is introduced
replacing inefficient KMnO4/pyridine as oxidant. The lowering of the HOMO level
is revealed as the determining factor for the trend in the adsorption energies
by electronic structure analysis.

Chemical Physics