Unusual Fluorescence of Unusual Fluorescence of Eu(III)Porphyrin EntrappedEu(III)Porphyrin Entrapped

In Sol-gel Silica MatrixIn Sol-gel Silica Matrix  

Stanisław Radzkia, Joanna Dargiewicz-Nowickaa, Magdalena Makarskaa and Janina

Legendziewiczb

aFaculty of Chemistry,

Maria Curie-Skłodowska UniversitybFaculty of ChemistryWrocław University

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.

Analytical applications of

porphyrins

Cu2+ T(1-MPy)PTPPS3

TPPT(3-MPy)PTMAPp-NO2Bz-TPPSCPIT(4-MPy)PTCPP

Cd2+ T(1-MPy)PATPPST(4-MPy)P

Zn2+ TPPS4

TPPS4

TPPTPPS4

Pd2+ TPPS4

Mg2+ T(4-MPy)P

Bi3+ TPPS4

Ag+ TPyP

Ni2+ TPPS4

Li+ OBTPPS

Hg2+ ATPPST(4-MPy)P

Pb2+ T(4-MPy)PTPPS3

Spectrophotometic metal determination

Analytical applications of

porphyrins

Other compounds determinated using porphyrins

pH OEP, OEPK, CP-TEE,CPK-TEE, N-MeEP,PdCP-SBH2TMePyP, H2TPPS4

Sn(IV)TPyP,Sn(IV)TMePyP

I- Zr(IV)TPPN,Co(II)TPPN

Cl- In(III)OEP

SCN- Zr(IV)TPPN,Co(II)TMePyPIn(III)OEP

Salicylan In(III)OEP

Aminy Co(III)TMePyP

Pirydyna Zr(IV)TPPN,Co(II)TPPNZnTPP

DNA TPPS4

Benzen TMePyP, DTMABP

Benzen,heksan, toluen

CuPaz(t-Bu)4

Lotne związkiorganiczne

Co-pNO2TPP,Rh(III)TPP

O2 Co(II)PBiałka hemowePt(II)OEP, Pd(II)OEPPt(II)OEPK,Pd(II)OEPKTPPRu(II)OEPZnTPP, ZnTFPP,ZnEtioP,ZnOEP, ZnTBPCoTPP

NO Białka hemowe

Cl2 Dimer porfiryny cynkut-SAP-Pporfiryna meso-tetra(p-stearamidofenylowa)

HCl TPPTP(OR)P gdzie R =CH3, n-C9H19, n-C8H17,CH2CH(C2H5)C4H9

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.

Porphyrin ring and its uv-vis

spectrum

NH N

NHN

5

10

15

20

meso

Sol-gel processing

basics

Alcohol metal

solution

HydrolysisPolicondenstion

Sol

coating

coat

ing

Gelation

percipitation

spinning

Ceramic fibers

Solvent removing

Evaporation

Xerogell

Glass,dense

ceramics

Aerogel

Heating

Dense filmHeating

Xerogel film

Wet gel

Unisized Gelled spheres

Oven

1. HYDROLYSISS i(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

Sol-gel methodCatalysator pH of

starting solution

Gelation timr (h)

HF 1.90 12 HCl 0.05 92

HNO3 0.05 100 H2SO4 0.05 106 HOAc 3.70 72 NH3 9.95 107 brak 5.00 1000

Element M(OR)n Si Si(OCH3)4

SiO(OC2H5)4 Al Al(O-izo C3H7)4

Al(O-sec C4H9)3 Ti Ti(O-C2H5)4

Ti(O-izo C3H7)4

Ti(O-C4H9)4

Ti(O-C5H7)4 B B(OCH3)3

Ge Ge(O-C2H5)4 Zr Zr(O-izo C3H7)4

Zr(O-C4H9)4 Y Y(O-C2H5)3 Ca Ca(O-C2H5)2

Sol-gel method advantages

• 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

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

EuTMePyP(acac) synthesis

Eu(acac)3 + H2TMePyP EuTMePyP(acac) + 2Hacac

[nm]

500 525 550 575 600 625 650 675 700 725 750 775 800 825 850 875 900

A

0,00

0,02

0,04

0,06

0,08

0,10

0,12

0,14

0,16

0,18

0,20

0,22

0,24

0,26

0,28

0,30

0,32

Zmiany widma absorpcji podczas syntezy EuTMePyP(acac)

[nm]

300 325 350 375 400 425 450 475 500

A

0,0

0,5

1,0

1,5

2,0

2,5

3,0

po ogrzaniu do wrzeniat = 1 ht = 2 ht = 3 ht = 4 h(w 24 h po zakoñczeniu reakcji)

EuTMePyP(acac)

NN

NN

N NN

N

CH3

CH3

CH3

CH3

+

+

+

+

OO

Eu

CH3CH3

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

EuTMePyP(acac)

EuP(acac) + 4H+ H4P2+ + Eu3+ + acac-

EuP(acac) + 3H2O Eu(OH)3 + Hacac + H2P

[nm]

300 350 400 450 500 550 600 650 700

A

0,00

0,25

0,50

0,75

1,00

1,25

1,50

1,75pH 8.0 pH 6.0 pH 4.0 pH 3.0 pH 1.8 pH 0.8

[nm]

475 500 525 550 575 600 625 650 675 700

A

0,000

0,025

0,050

0,075

0,100

420nm420nm421nm431nm428nm440nm

pH 8.0 pH 6.0 pH 4.0 pH 3.0 pH 1.8 pH 0.8

554nm553nm554nm559nm

520nm558nm

589nm 636nm

EuTMePyP(acac)Pasmo Soreta

Pasmo Q

H2TMePyP

[nm]

300 350 400 450 500 550 600 650 700

A

0,00

0,25

0,50

0,75

1,00

1,25

1,50

1,75

Pasmo Q 10 x

Pasmo Soreta

H2O 423.1

MeOH 424.7EtOH 425.8DMSO 425.5 DMF 425.4

518.9516.4517.6517.1516.7

555.5552.9554.3552.2552.6

586.2591.9593.3589.2588.9

642.0651.0649.0643.8644.9

Eu(III)TMePyP(acac)

[nm]

300 350 400 450 500 550 600 650 700

A

0,00

0,25

0,50

0,75

1,00

1,25

1,50

1,75

2,00

Pasmo Q 10 x

Pasmo Soreta

H2O 420.3

MeOH 424.2EtOH 424.8DMSO 431.8 DMF 430.6

553.2557.1556.2563.1563.1

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

solvents

H2TMePyP – excitation and

emission spectra

H2TMePyP and EuTMePyP(acac) uv-vis spectra in

hydrogel

[nm]

300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700

A

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

1,1 Pasmo Q~ 15 x

Pasmo Soreta 428 nm

520 nm

553 nm

546 nm

590 nm

EuTMePyP(acac)

H2TMePyP

EuTMePyP(acac)(czêœciowo roz³o¿ony)

417 nm542 nm

426 nm550 nm

Excitation spectra of H2TMePyP,

EuTMePyP(acac) and EuCl3

Fluorescence spectra of H2TMePyP,

EuTMePyP(acac) and EuCl3

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

Porphyrin monolayer

formation on the silica gel

surface

N

N

N

N

N N

NN

H

H

OH

O

O

O

Si CH2Cl +

N

N

N

N

N N

NN

H

H

OH

O

O

O

Si CH2

+*Cl -

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.