Synthesis and Spectral Properties of Zr(Iv) and Hf(Iv) Phthalocyanines with Beta-Diketonates As Axial Ligands

The series of new zirconium(IV) and hafnium(IV) phthalocyanines with various beta-dicarbonyl ligands were prepared via direct interaction between di(chloro) zirconium(IV) or hafnium(IV) phthalocyanines and free b-diketones and also with 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one. The structure of the obtained bis(beta-dicarbonilato) zirconium(IV) and hafnium(IV) phthalocyanines was studied by two dimension H-1 NMR spectroscopy (COSY, NOESY, ROESY). Absorption and fluorescence spectroscopic studies have been investigated in various solvents. Analyzed compounds of concentration range below 10-5 mol/dm 3 do not aggregate in the organic solvents. Fluorescence quantum yields (Phi(F)) and natural life times (tau) of zirconium phthalocyanine complexes have been calculated in toluene, DMSO and THF. (C) 2007 Elsevier B.V. All rights reserved.