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Unusual Fluorescence of Eu(III)Porphyrin Entrapped In Sol-gel Silica Matrix

Unusual Fluorescence of Eu(III)Porphyrin Entrapped In Sol-gel Silica Matrix. St anisław Radzki a , J oanna Dargiewicz-Nowicka a , M agdalena Makarska a and J anina Legendziewicz b a Faculty of Chemistry, Maria Curie-Skłodowska University b Faculty of Chemistry Wrocław University.

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Unusual Fluorescence of Eu(III)Porphyrin Entrapped In Sol-gel Silica Matrix

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  1. Unusual Fluorescence of Eu(III)Porphyrin EntrappedIn Sol-gel Silica Matrix Stanisław Radzkia, Joanna Dargiewicz-Nowickaa,Magdalena Makarskaa and Janina Legendziewiczb aFaculty of Chemistry, Maria Curie-Skłodowska University bFaculty of Chemistry Wrocław University

  2. Porphyrin importance • Porphyrins and their derivatives are widely applied in analytical chemistry. They can be used for analysis of cations, anions, organic compounds and gases. Methods are mostly based on porphyrin spectral and electrochemical properties. • Energy transfer systems (solar energy, PDT). • Possibility of the entrapment of organic reagents into sol-gel monolithic matrices and thin coatings. A new unique hybrid material (mixed organic and inorganic compounds) can be applied in chemo- and biosensors.

  3. Analytical applications of porphyrins Spectrophotometic metal determination

  4. Analytical applications of porphyrins Other compounds determinated using porphyrins

  5. Aim of this work • Method of the preparation of cationic porphyrin doped silica gels. • Europium(III) porphyrin complex synthesis. • Spectral characterisation of the cationic porphyrin and its Eu(III) complex in solutions and monolithic gel.

  6. Porphyrin ring and its uv-vis spectrum

  7. Alcohol metal solution Hydrolysis Policondenstion Sol-gel processing basics Xerogel film Dense film Heating coating Glass, Wet gel dense Xerogell ceramics Heating coating Evaporation Aerogel Gelation Solvent removing Unisized Gelled spheres percipitation spinning Sol Oven Ceramic fibers • 1. HYDROLYSIS • Si(OR)4 + nH2O  (OR)4-n-Si-(OH)n + nROH • 2. CONDENSATION • (RO)3Si-OR + HO-Si(OR)3 (RO)3Si-O-Si(OR)3 + ROH • (RO)3Si-OH + HO-Si(OR)3 (RO)3Si-O-Si(OR)3 + H2O

  8. Sol-gel method

  9. Sol-gel methodadvantages • Material homogenization • High purity • Mixing in the atomic scale of the various compounds (possibility of organic material addition) • Good control over surface or powder size

  10. TEOS(tetraethyl orthosilicate) • Si(OC2H5)4 + nH2O  (OC2H5)4-n-Si-(OH)n + nC2H5OH • (C2H5O)3Si-OC2H5 + HO-Si(OC2H5)3 (C2H5O)3Si-O-Si(OC2H5)3 + C2H5OH • (C2H5O)3Si-OH + HO-Si(OC2H5)3 (C2H5O)3Si-O-Si(OC2H5)3 + H2O

  11. EuTMePyP(acac) synthesis Eu(acac)3 + H2TMePyP  EuTMePyP(acac) + 2Hacac

  12. EuTMePyP(acac) Europium(III)(meso-tetrakis(1-methyl-4-pirydyl)porphyrin) acetylacetonate)

  13. EuTMePyP(acac) EuP(acac) + 4H+H4P2+ + Eu3+ + acac- EuP(acac) + 3H2O  Eu(OH)3 + Hacac + H2P

  14. H2TMePyP and EuTMePyP(acac) uv-vis absorption spectra in various solvents

  15. H2TMePyP – excitation and emission spectra

  16. H2TMePyP and EuTMePyP(acac)uv-vis spectra in hydrogel

  17. Excitation spectra of H2TMePyP, EuTMePyP(acac) and EuCl3

  18. Fluorescence spectra of H2TMePyP, EuTMePyP(acac) and EuCl3

  19. Conclusion • Synthesis of the EuTMePyP(acac) complex not earlier described in the literature • No fluorescence in solutions • Strong fluorescence emission in hydrogel, probably due to the „axial ligand exchange” or silica-Eu(III)P reaction

  20. Porphyrin monolayer formation on the silica gel surface D. Delmarre, R. Meallet, C. Bied-Charreton, R.B. Pansu: “Heavy metal ions detection in solution, in sol-gel and with grafted porphyrin monolayers”, J. Photochem. and Photobiol. A, 1999, 124, 23.

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