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 (SO 2 C 8 H 17 ) and donor (OC 8 H 17 ) substituents. The UV−vis spectra of compounds 2a − e in CHCl 3 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 π-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 1 H NMR spectra.