Novel homo- and heterodimetallic heterobinuclear phthalocyaninato-triazolehemiporphyrazinate complexes

A family of unsymmetrical heterobinuclear phthalocyaninato-triazolehemiporphyrazinate (Pc-Thp) complexes 2a-e has been synthesized for the first time by statistical mixed condensation of regioisomerically pure dicyanotriazolehemiporphyrazinates 5a,b with differently substituted phthalonitrile derivatives 6 and 7. This stepwise approach allows to prepare heterodimetallic complexes 2b and 2d incorporating Ni(II) or Zn(II) in the cavity of each macrocyclic unit as well as a "push-pull" homodimetallic Pc-Thp compound, 2e, bearing acceptor (SO2C8H17) and donor (OC8H17) substituents. The W-vis spectra of compounds 2a-e in CHCl3 exhibit a broad and split Q-band indicative of intra- and intermolecular interactions. Moreover, a strong red-shifting (25-50 nm) relative to the;octasubstituted mononuclear Pc compounds is observed, which is in agreement with the enlargement of the pi-conjugated Pc system. Interestingly, the optical behavior of Pc-Thp compounds 2a-d is driven by the central metal included into the Pc moiety. Compound 2e exhibits a low degree of intermolecular interactions in solution taking into account its UV-vis and H-1 NMR spectra.