Spectroscopic Characterization of Porphyrins Entraped in Sol-gel Silica Matrix Joanna Dargiewicz-Nowicka, Magdalena Makarska, Stanisław Radzki Department.

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Presentation transcript:

Spectroscopic Characterization of Porphyrins Entraped in Sol-gel Silica Matrix Joanna Dargiewicz-Nowicka, Magdalena Makarska, Stanisław Radzki Department of Inorganic Chemistry Maria Curie-Skłodowska University in Lublin

Porphyrin importance 1.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. 2. Energy transfer systems (solar energy, PDT). 3. 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.

Analytical applications of porphyrins Spectrophotometic metal determination

Analytical applications of porphyrins Other compounds determinated using porphyrins

Porphyrin ring and its uv-vis spectrum

Sol-gel method

Sol-gel method advantages 1.Material homogenization. 2.High purity. 3.Mixing in the atomic scale of the various compounds. 4.Good control over surface or powder size. Conclusion 1. Synthesis of the EuTMePyP(acac) complex not earlier described in the literature. 2. No fluorescence in solution. 3. Strong fluorescence emission in hydrogel, probabely due to the „axial ligand exchange” or silica-Eu(III) reaction.

TEOS (tetraethyl orthosilicate) Si(OC 2 H 5 ) 4 + nH 2 O  (OC 2 H 5 ) 4-n -Si-(OH) n + nC 2 H 5 OH (C 2 H 5 O) 3 Si-OC 2 H 5 + HO-Si(OC 2 H 5 ) 3  (C 2 H 5 O) 3 Si-O-Si(OC 2 H 5 ) 3 + C 2 H 5 OH (C 2 H 5 O) 3 Si-OH + HO-Si(OC 2 H 5 ) 3  (C 2 H 5 O) 3 Si-O-Si(OC 2 H 5 ) 3 + H 2 O

EuTMePyP(acac) synthesis Eu(acac) 3 + H 2 TMePyP  EuTMePyP(acac) + 2HacacEuTMePyP(acac) EuP(acac) + 4H +  H 4 P 2+ + Eu 3+ + acac - EuP(acac) + 3H 2 O  Eu(OH) 3 + Hacac + H 2 P

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

H 2 TMePyP and EuTMePyP(acac) uv-vis absorption spectra in various solvents

H 2 TMePyP – excitation and emission spectra

H 2 TMePyP and EuTMePyP(acac) uv-vis spectra in hydrogel

Fluorescence spectra of H 2 TMePyP, EuTMePyP(acac) and EuCl 3 Excitation spectra of H 2 TMePyP, EuTMePyP(acac) and EuCl 3

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.