Novel Homo- and Heterodimetallic Heterobinuclear Phthalocyaninato-Triazolehemiporphyrazinate Complexes

• Published in: Journal of organic chemistry 1998-11, Vol.63 (24), p.8888-8893
• Main Authors: de la Torre, Gema, Martínez-Díaz, M. Victoria, Ashton, Peter R, Torres, Tomás
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo981118p

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 UV−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 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 1H NMR spectra.