The effect of phthalocyanine molecule structure on its photo-induced production of singlet oxygen species

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1 ISTITUTE F CHEMICAL TECHLGY I PRAGUE FACULTY F CHEMICAL TECHLGY Department of rganic Technology The effect of phthalocyanine molecule structure on its photo-induced production of singlet oxygen species Martin Drobek, PhD Research Institute for rganic Syntheses, Pardubice

2 Structure of phthalocyanines R.P.LISTEAD (933) Phthalocyanine U H H Superphthalocyanine B X Subphthalocyanine aphtha mineral oil Cyanine dark blue M L M L M L M F. H. Moser, A. L. Thomas: The Phthalocyanines, Vol. I and II, CRC Press, Boca Raton, Fla. 3343, 983. F. H. Moser, A. L. Thomas: Phthalocyanine Compounds. Reinhold Publ. Co., ew York, London 963.

3 Applications of phthalocyanines Direct Photocatalysts Pigments and dyes Auxiliary compounds Liquid crystals Special chemicals Photooxidation of pollutants Photodynamic drugs Chemical sensors Semiconductors Photovoltaic and solar cellsc C. C. Leznoff, A. B. P. Lever: Phthalocyanines, Properties and Applications, Weinheim 993

4 Aim of the work Preparation of phthalocyanines (derivatives) Study of spectral behaviour of sulphonated derivatives phthalocyanines in solution Testing of production of singlet oxygen polychromatic monochromatic light sources P. Klusoň, M. Drobek, S. Krejčíková, J. Rakušan: Appl. Catal. B 8, 32 (28). P. Klusoň, M. Drobek, T. Strašák, J. Rakušan: J. Mol. Catal. A: 272, 23 (27). M. Drobek, P. Klusoň, J. Rakušan: Res. Chem. Intermediat. (27) - submitted. P. Klusoň, M. Drobek, A. Kalaji, J. Rakušan: J. Photochem. Photobiol. A (27) - submitted.

5 Synthesis and modification of phthalocyanines Solvent-free process + H 2 H 2 MeCl 2 cat Solvent process C C + MeCl 2 nitrobenzene ammonia cat Me C + MeCl 2 CH 3 a C octanol Sulfonation Me Fuming sulphuric acid Me ClS 3 H, SCl 2

6 Photosensitized reactions of oxygen Photosenzitizers - (n π*) Photosenzitizers - (ππ*) 3 MPc* MPc + 3 MPc* + Subs Subs + + MPc - MPc - + MPc H + H H + Subs-H H 2 + Subs Subs + + Subs + H 2 + H xidation products MPc MPc* 3 MPc* 3 MPc* MPc + Subs xidation products Mechanism of production of S ics ( Σ g ) hv f ic ( g ) hv hv f ic hv p isc hv p isc hv p isc S 2 ( 3 Σ g )

7 Testing of phthalocyanines in production of Catalytic decomposition of chlorophenols in aqueous phase polychromatic light sources phenol 2-chlorophenol 3-chlorophenol 4-chlorophenol 2,6-dichlorophenol 2,4,6-trichlorophenol Cl x H / H - - HCl H H / H - -C C- + HC- + C 3 2- Experimental setup Emission spectra Analytical 6,E+5 3,E+5 Light sources ARVA SPECIAL (8W) ARVA Blacklight Blue (8W) Titrator Manager TIM 856, TitraLab,E wave lenght [nm],e+5 5,E+4,E wave length[nm] HPLC chromatograph Shimadzu LC 2A prominence column Lichrospher length cm diameter.6 cm thickness of stationary phase 5µm

8 Decomposition of chlorophenols - visible light (J hv =7.37 Einstein s - cm -2 ) polychromatic light sources UV light (J hv =5,3 Einstein s - cm -2 ) -ln(c/co) AlPc ZnPc SiPc MFFPc CoPc ipc CuPc TiPc FePc Pc(S3a)mix Al 5 5 t (min) Si Zn -ln(c/c o) 4 3,6 3,2 2,8 2,4 2,6,2,8,4 AlPc ZnPc SiPc MFPc CoPc Pc a) mix Al Al Si ipc CuPc TiPc FePc 5 5 t (min) Si Zn Pseudo-first order kinetics Quantum yield c = c o exp (-kt) Intensity of photon flux m = 7. x Pc -6 mol/dm 3 c 4-CP = x -4 mol/dm 3 ph = Irradiation intenzity φ 4 Ph k V c J A = 4 Ph 4 Ph hν J hν 2 [ einstein s ] λ Pf = m h c A P f = I S 2 [ W m ] Si photodiode Hamamatsu S337-BQ)

9 Decomposition of chlorophenols - polychromatic light sources visible light (J hv =7.37 Einstein s - cm -2 ) 2 AlPc a) mix Q -ln(c/co) AlPc ZnPc SiPc MFFPc CoPc ipc CuPc TiPc FePc Pc(S3a)mix A UV B VIS t (min) wave lenght (nm) VIS region UV - region ph k [min - ] Φ 4-CP [%] k [min - ] Φ 4CP [%] AlPc a) mix. x x -2. SiPc a) mix 9.5 x x ZnPc a) mix 5. x x -3.3

10 Photooxidation using monochromatic light sources Experimental setup optical bench High-pressure Hg výbojka (Aec Lamp -LSB64 (Lot-riel), 5 W. cptical filters Wave lenght 34, 365, 44, 435, 6, 632 a 67 Hg lamp ptical filters with holder shutter (nm)

11 Decomposition of 4-chlorophenol - monochromatic light Al Decomposition of 4-chlorophenol 67 nm Deuterated water (solvent) wave lenght (nm).2 Pc A.8 Zn AlPc Ф (%).8 Ф (%) 5.3 Ф (%) Si wave lenght (nm)) SiPc ZnPc c 4-CP =. x -4 mol/dm 3 c Pc = 7. x -6 mol/dm 3 ph = Pcs VIS 67 nm 632 nm 6 nm 435 nm 44 nm 365 nm UV AlPc SiPc ZnPc

12 Influence of solvent to the reaction rate photooxidation - monochromatic light source Addition of alcohol to the reaction mixture -ln(c/co) chlorophenol water % water:ethanol : ethanol % Zn -ln(c/co).7.35 water ethanol water:ethanol : H H t (min) Absorption spectrum ZnPc t (min) Absorption spectrum MFPc c CP =. x -4 mol/dm 3 c Pc = 7. x -6 mol/dm 3 UV-VIS spectrophotometer (Cary UV-VIS, Varian

13 Influence of solvent to the reaction rate photooxidation - monochromatic light source Addition of alcohol to the reaction mixture -ln(c/co) water % water:ethanol : ethanol % 4-chlorophenol t (min) Zn Quantum Yield (% H2 % Ethanol % Quantum Yields for ZnPc at 67 nm Ethanol % Water % Quantum yield 67 nm nm

14 Physical-chemical chemical methods of singlet oxygen detection chemical quenchers Me 9,- dimethyanthracene A wave length (nm) Quantum yield Ф [%] AlPcSmix 5. Phthalocyanine SiPcSmix ZnPcSmix ZnPc 2.9 c DMA =.45 x -4 mol/dm 3 c FTC = 7. x -6 mol/dm 3 5 4,5 4 3,5 SiPcSmix AlPcSmix ZnPcSmix ZnPc Experimental setup Spektrophotometr UV mini 24 Shimadzu -ln(c/c o) 3 2,5 2,5, t (min) quartz cell (3,5 ml) wave length 67 nm absorbance decrease (399 nm)

15 Acknowledgement Ing. Jan Rakušan, CSc Ing. Marie Karásková Alena Hyhlánová Marie Štěpánková Ing. Pavla Vlasáková Doc. Ing. Josef Krýsa Ph.D Ing. Tomáš Strašák Ing. Simona Krejčíková Šárka Zárubová Jaroslav Šourek Ali Kalaji Financial support GA ČR 4/4/963 MP ČR FT-TA/23 GA ČR 23/3/H4 GA ČR HMP KA4727 MŠMT ČR anopin M