Synthesis and spectral properties of Zr(IV) and Hf(IV) phthalocyanines with β-diketonates as axial ligands

• Published in: Inorganica Chimica Acta Vol. 361; no. 9; pp. 2569 - 2581
• Main Authors: Tomachynski, L.A., Tretyakova, I.N., Chernii, V.Ya, Volkov, S.V., Kowalska, M., Legendziewicz, J., Gerasymchuk, Y.S., Radzki, St
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 27.06.2008
• Subjects: 2D NMR spectroscopy; Electronic absorption and emission spectra; Fluorescence; Hafnium(IV); Phthalocyanine; Zirconium(IV); β-Diketones; Hafnium(IV); Phthalocyanine; Electronic absorption and emission spectra; Zirconium(IV); Fluorescence; 2D NMR spectroscopy; β-Diketones
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2007.11.003

Zirconium(IV) and hafnium(IV) phthalocyanines with β-dicarbonyl ligands were prepared via direct interaction between di(chloro)zirconium(IV) or hafnium(IV) phthalocyanines and free β-diketones and also with 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one. The structure of the obtained bis(β-dicarbonilato) zirconium(IV) and hafnium(IV) phthalocyanines was studied by two dimension 1H NMR spectroscopy (COSY, NOESY, ROESY). The series of new zirconium(IV) and hafnium(IV) phthalocyanines with various β-dicarbonyl ligands were prepared via direct interaction between di(chloro)zirconium(IV) or hafnium(IV) phthalocyanines and free β-diketones and also with 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one. The structure of the obtained bis(β-dicarbonilato) zirconium(IV) and hafnium(IV) phthalocyanines was studied by two dimension 1H 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 ( Φ F) and natural life times ( τ) of zirconium phthalocyanine complexes have been calculated in toluene, DMSO and THF.