Zirconium(IV) and hafnium(IV) phthalocyanines with various phthalic acids as axial ligands: synthesis and properties



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Zirconium(IV) and hafnium(IV) phthalocyanines with various phthalic acids as axial ligands: synthesis and properties.
1V.Ya.Chernii, 1L.A.Tomachynski, 2Yu.S.Gerasymchuk, 1S.V.Volkov, 2S.Radzki

1I.V.Vernadskii Institute of General and Inorganic Chemistry, 32/34 Palladin ave., Kiev, Ukraine, e-mail: mitya@ionc.kar.net.

2Faculty of Chemistry, M.Curie-Sklodowska University, sq. M.Curie-Sklodowska 2, 20-031 Lublin, Poland.
Di(chloro)zirconium(IV) and -hafnium(IV) phthalocyanines are known to react easily with different β-diketones and polyphenol compounds. The mixed ligand complexes are formed as the results of reactions. These complexes in depending on nature of ligands have various properties: stability, solubility in different solvents, tendency to aggregation [1,2].

T
his work is devoted to the synthesis of zirconium (IV) and hafnium(IV) phthalocyanines with axial coordina-ted phthalic, trimellitic, pyromellitic acids and studying of their spectral properties in water, alcohol, and DMSO.

These complexes were obtained by the reaction between di(chloro)zirconium(IV) and -hafnium(IV) phthalocyanines and corresponding acids. The synthesis was carried out by the method reported in [1]. All obtained complexes are blue-green substances and have composition PcML (where M = Zr, Hf) by the data of element analyzes. The introducing of carboxylic groups in axial fragment leads to increase of solubility of synthesized complexes. This tendency is observed especially bright in water solutions.

UV-vis spectra of obtained phthalocyanines registered in alcohol and DMSO are typical patterns for monomer metallophthalocyanines. They show Soret, satellite, and Q- bands about 340, 620, 690 nm respectively. The described compounds are aggregated in water solutions. Changing of intensities of satellite and Q-band also shift of their position to hypso- and batochromic regions consequently take place. In mixtures of water-alcohol and water-DMSO aggregative processes are observed when water content in system is 50% and more.

Thus, the novel water soluble mixed ligand phthalocyanine complexes of zirconium and hafnium with various phthalic acids were obtained. It is shown that the introducing of axial ligands, containing hydrophilic groups, to the central atom of phthalocyanine system increases solubility these complexes in water solution and other solvents.

1. L.A.Tomachynski, V.Ya.Chernii, S.V.Volkov, J. Porph. Phthalocyanines, 10 (2001) 731.



2. L.A.Tomachynski, V.Ya.Chernii, S.V.Volkov, J. Porph. Phthalocyanines, 6 (2002) 90.
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