SPECTROSCOPIC CHARACTERIZATION OF GALLATE PHTHALOCYANINES OF ZIRCONIUM(IV) AND HAFNIUM(IV) IN SILICA GELS Gerasymchuk Y. 1, Chernii V. 2, Tomachynski L. 2, Legendziewicz J. 3, Radzki S. 1 1 Faculty of Chemistry, Maria Curie-Sklodowska University, Lublin, Poland 2 V.I.Vernadskii Institute of General and Inorganic Chemistry, 32/34 Palladin ave., Kiev, Ukraine. 3 Faculty of Chemistry, Wrocław University, 14 F. Joliot-Curie str., Wrocław, Poland

Investigated complexes M(IV)= Zr, Hf

General properties and applies of phthalocyanine dotted sol-gel materials For over 30 years phthalocyanine dyes have been extensively studied due to their spectroscopic and photoelectric properties and can be applied in many branches: in the field of physics, in technique, medicine, chemistry and other sciences, Metallophthalocyanine compounds have attracted special attention due to their unique properties such as conductivity electrochromism and variety of catalytic function. Phthalocyanines are characterized by significant absorption in the visible region, large absorption coefficient, and high thermal and photochemical stability. For that reason they are good potential candidates in solar-to-electric energy conversion and as modulators of light energy in laser devices. As model system for phthalocyanine basic solar-to-electric energy converters, optical data carriers, chemical sensors and laser devices we can use sol-gel materials doped by metalloporphyrins and its analogues – metalophthalocyanines. It is a new mixing organic and inorganic hybrid material with unique physical, chemical and optical properties. Sol-gel monolith and sol-gel thin films are very useful to encapsulate various guests such as inorganic clusters, lanthanide complexes, laser dyes etc. Different complexes including metalloporphyrin and metallophthalocyanine based systems have also been encapsulated by sol-gel processing to give hybrid organic-inorganic. Application of the metalroporphyrins and metalophthalocyanines dotted sol-gel materials as catalyst of oxidation of alkenes, aromatic, halogenoorganic and other organic and inorganic compounds have been also reported. Moreover, sol-gel materials have been intensively investigated as host media to encapsulate different spacious biological materials, including enzymes, catalytic antibodies, proteins, polynucleic acids, microbials, animal cells and plants for applications in byocatalysis, immunodiagnostics, bioptical devices and as biosensors or bioimplants.

Description of experiment We presented our study of the water soluble axially gallate substituted phthalocyanines with zirconium and hafnium as central coordinate metals encapsulation in the monolith gels obtained by sol-gel method. The samples of dried gels with different concentration of phthalocyanine complexes were prepared by hydrolysis of tetraethoxysilane (TEOS) and following cocondensation with investigated complexes. The changes in the absorption and emission spectra at the different stages of gel drying presented in the comparison of absorption and emission spectra for solutions of complexes in EtOH, DMSO, water and in the mixtures of these solvents.

Absorption spectra of the PcZr(IV)gallate in solutions, and in gel on different stages of gelating process 5·10 -5 M/dcm 3

Absorption spectra of PcHf(IV)gallate in solutions, and in gel on different stages of gelating process 5·10 -5 M/dcm 3.

Band maxima wawelenghts of PcZr(IV)gallate in solutions, and in silica gels on different stages of gelating process Absorption maxima 2.5·10 -6 [M/dcm 3 ] 5·10 -6 [M/dcm 3 ] 1·10 -5 [M/dcm 3 ] 2·10 -5 [M/dcm 3 ] 4·10 -5 [M/dcm 3 ] PcZr(IV)Gallate in solutions SQSQSQSQSQ H2OH2O EtOH DMSO DMSO : H 2 O DMSO : EtOH PcZr(IV)Gallate in silica gels SQSQSQSQSQ Before geling ~693 After geling ~690 Drying 1 month ~686 Driyng 1 year

Band maxima wawelenghts of PcHf(IV)gallate in solutions, and in silica gels on different stages of gelating process Absorption maxima 2.5·10 -6 [M/dcm 3 ] 5·10 -6 [M/dcm 3 ] 1·10 -5 [M/dcm 3 ] 2·10 -5 [M/dcm 3 ] 4·10 -5 [M/dcm 3 ] PcHf(IV)Gallate in solutions SQSQSQSQSQ H2OH2O EtOH DMSO DMSO : H 2 O DMSO : EtOH PcHf(IV)Gallate in silica gels SQSQSQSQSQ Before geling ~695 After geling ~694 Drying 1 month ~695 Driyng 1 year

Comparison of the absorption, excitation and emission spectra of PcZr(IV)Gallate in silica matrix 2·10 -5 and 4·10 -5 M/dcm 3.

Comparison of absorption, excitation and emission spectra of PcHf(IV)Gallate in silica matrix 2·10 -5 and 4·10 -5 M/dcm 3.