Novel d- and f-metal phthalocyaninates based on 4-(2,4,5-trichlorophenoxy)phthalonitrile. Synthesis, spectroscopic and fluorescent properties

The work reports synthesis and spectroscopic-luminescent properties of first obtained zinc, magnesium, erbium and gadolinium trichlorophenoxy-phthalocyanine complexes. The initial building unit being 4-(2,4,5-trichlorophenoxy)phthalonitrile is synthesized by nucleophilic substitution reaction. Zinc and magnesium complexes are obtained by template condensation of the phthalodinitrile and corresponding acetates. A demetallization of magnesium phthalocyaninate results in the formation of free tetra-4-(2,4,5-trichlorophenoxy)phthalocyanine ligand. Rare-earth element complexes are synthesized by two approaches: template condensation and metallization of free phthalocyanine ligand. The planar complex is found to be yielded higher in case of template fusion. Influence of lanthanide salts anion (acetate, chloride) on formation ability of sandwich-type complex is analyzed. A double-decker complex is testified to be formed only upon the template fusion of gadolinium acetate with 4-(2,4,5-trichlorophenoxy)phthalonitrile. The as-obtained compounds are studied in terms of spectral-luminescent characteristics. A bathochromic shift of absorption Q-band maximum is found to accompany d-to-f-metal transition. The zinc complex being associated in chloroform exhibits higher quantum yield of fluorescence than monomeric forms generated upon addition of organic ligand.