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

1Faculty of Chemistry, Maria Curie-Sklodowska University,20-031 Lublin, Poland

2V.I.Vernadskii Institute of General and Inorganic Chemistry, 32/34 Palladin ave., Kiev, Ukraine.

3Faculty of Chemistry, Wrocław University, 14 F. Joliot-Curie str., 50-383 Wrocław, Poland

gerasymchuk_y@ukrpost.net

Investigated complexes

O

O

O

O

O

N

NN

NNN NN

M(IV)

H

H

H

H

H

H HH

H

H

HH

H HH

H

H

H

H

H

M(IV)= Zr, Hf

General properties and applies of phthalocyanine dotted sol-gel materialsFor 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 experimentWe 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/dcm3

nm300 400 500 600 700 800

A

0.0

0.2

0.4

0.6

0.8Before gelingAfter gelingDrying after monthDrying after yearH2O solution

DMSO solutionEtOH solution

Absorption spectra of PcHf(IV)gallate in solutions, and in gel on different stages of gelating process 5·10-5 M/dcm3.

nm300 400 500 600 700 800

A

0.0

0.2

0.4

0.6

0.8Before gelingAfter gelingDrying after monthDrying after yearEtOH solutionH2O solution

DMSO solution

Band maxima wawelenghts of PcZr(IV)gallate in solutions, and in silica gels on different stages of gelating processAbsorption maxima

2.5·10-6 [M/dcm3]

5·10-6 [M/dcm3]

1·10-5 [M/dcm3]

2·10-5 [M/dcm3]

4·10-5 [M/dcm3]

PcZr(IV)Gallatein solutions

S Q S Q S Q S Q S Q

H2O 337 690 337 690 337 690 337 690 337 690

EtOH 339 682 339 682 339 682 339 682 339 682

DMSO 350 690 350 690 350 690 350 690 350 690

DMSO : H2O 342 691 342 691 342 691 342 692 342 692

DMSO : EtOH 343 688 345 688 345 688 345 689 345 689

PcZr(IV)Gallatein silica gels

S Q S Q S Q S Q S Q

Before geling 351 694 349 694 350 694 350 693 350 ~693

After geling 349 694 349 695 347 694 347 688 347 ~690

Drying 1 month - 694 - 696 345 694 344 689 342 ~686

Driyng 1 year - 692 - 692 - 690 337 689 336 685

Band maxima wawelenghts of PcHf(IV)gallate in solutions, and in silica gels on different stages of gelating processAbsorption maxima

2.5·10-6 [M/dcm3]

5·10-6 [M/dcm3]

1·10-5 [M/dcm3]

2·10-5 [M/dcm3]

4·10-5 [M/dcm3]

PcHf(IV)Gallate in solutions

S Q S Q S Q S Q S Q

H2O 346 701 346 701 346 701 346 701 346 701

EtOH 349 686 349 686 349 686 349 686 349 686

DMSO 347 686 347 686 347 686 347 686 347 686

DMSO : H2O 345 700 345 700 345 701 346 700 346 699

DMSO : EtOH 350 685 351 685 351 686 351 686 351 686

PcHf(IV)Gallate in silica gels

S Q S Q S Q S Q S Q

Before geling 352 694 351 693 350 694 349 695 349 ~695

After geling 351 694 351 694 350 694 347 694 348 ~694

Drying 1 month 346 694 348 694 349 694 345 695 346 ~695

Driyng 1 year - 691 - 691 342 688 339 688 343 688

Comparison of the absorption, excitation and emission spectra of PcZr(IV)Gallate in silica matrix 2·10-5 and 4·10-5 M/dcm3.

Comparison of absorption, excitation and emission spectra of PcHf(IV)Gallate in silica matrix 2·10-5 and 4·10-5 M/dcm3.