Synthesis and luminescent properties of new zirconium(IV) and hafnium(IV) phthalocyanines with various carbonic acids as out-planed ligands

A range of zirconium(IV) and hafnium(IV) phthalocyanines with various carboxylic acids as out-planed ligands has been synthesized by a direct interaction between di(chloro)zirconium(IV)- or hafnium(IV)-phthalocyanines and carboxylic acids. Coordination of two acid fragments is suggested to occur in a cis-geometry about the central atom of the macrocycle as evidenced on the basis of 1H NMR, UV–vis and elemental analysis data. Absorption and fluorescence spectroscopic studies have been analyzed in different solvents. These compounds are non-aggregated in the organic solvents. Fluorescence quantum yields (ΦF) and natural lifetimes (τ) of zirconium phthalocyanine complexes have been calculated in toluene and DMSO.