Yeni Flor Zincirli Çözünür Ftalosiyaninler: Sentezi, Karakterizasyonu, Fotokimyasal ve Fotofiziksel Özellikleri

B u çalışmada yeni 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10 3-nitroftalonitril ve onun çözünebilir non-peripheral çinko II 2 , magnezyum II 3 , kobalt II 4 ve indiyum klorür III 5 ftalosiyanin türevlerinin sentezi ilk kez rapor edildi. Yeni sentezlenmiş metalo ftalosiyanin türevlerinin yapıları, kütle, UV-Vis, FT-IR, ve 1H-NMR spektroskopisi kullanılarak karakterize edildi. Fotokimyasal Singlet Oksijen foto bozunma kuantum verimleri ve fotofiziksel floresans kuantum verimleri özellikleri tetrahidrofuran THF içinde incelendi. Flor atomları taşıyan uzun alkil zincirli gruplar taşıyan metallo fitalosiyaninlerin , THF, diklorometan DCM , kloroform CHCI3 ve toluen gibi bilinen organik çözücülerde yığılma göstermeden yüksek çözünürlüğe sahip oldukları görüldü. Bunun yanı sıra, merkez metal iyon türü ve substitüentin pozisyon etkisi daha önceki çalışmalarla karşılaştırılarak çalışıldı. Non peripheral konumun fotofiziksel ve fotokimyasal özellikleri geliştirdiği gözlendi

Anahtar Kelimeler:

Ftalosiyaninler, fotofizik, fotokimya

Novel, Highly Soluble Non-Peripherally Phthalocyanines Bearing Bulky Groups Containing Fluorine Atoms: Synthesis, Characterization, Spectral and Improved Photophysicochemical Properties

The synthesis of a new phthalonitrile 1 was described by treating 3-nitrophthalonitrile with 4- 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecylthio phenol. After that, its soluble zinc II 2 , magnesium II 3 , cobalt II 4 and indium chloride III 5 non-peripheral phthalocyanine derivatives were reported for the first time. The newly synthesized metallo phthalocyanine derivatives were characterized by mass spectrometry, UV-Vis, FT-IR, and 1H-NMR spectroscopy. Photochemical and photophysical photodegradation, singlet oxygen and fluorescence quantum yields properties of the phthalocyanines were carried out in tetrahydrofuran THF . Metallo-phthalocyanines, which containing a bulky long alkyl chain bearing fluorine atoms, have high solubility in known organic solvents such as THF, dichloromethane DCM , chloroform CHCl3 and toluene and do not show aggregation. Besides, the effect of metal ion types in phthalocyanines core 2, 3, 4 and 5 were also investigated. The effects of the substitution with fluoroalkynyl-functionalized groups on these parameters mentioned were also compared along with the previously synthesized peripherally tetra and octa substituted phthalocyanines. Non peripherally position of the substituents on Pc improved photophysical and photochemical properties.

Keywords:

Phthalocyanines, photophysic, photochemistry,

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1. P.A. Stuzhin, O.G. Khelevina, S.Angeoni, B.D. Berezin, in: C.C. Leznoff, A.B.P. Lever, Properties and Applications, 1996, VCH: vol. 4.
2. P.A. Stuzhin, Azaporphyrins and phthalocyanines as multicentre conjugated ampholites, J. Porphyr Phthalocya, 3 (1999) 500.
3. E. Kırbaç, G. Yaşa Atmaca, A. Erdoğmuş, Novel highly soluble fluoro, chloro, bromo-phenoxyphenoxy substituted zinc phthalocyanines; synthesis, characterization and photophysicochemical properties, J. Organomet. Chem., 752 (2014) 115
4. T.F. Dougherty, Photodynamic therapy (PDT) of malignant tumors, Crit. Crit. Rev. Oncol. Hematol., 2 (1984) 83.
5. T. Nyokong, Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines, Coordin. Chem. Rev., 251 (2007) 1707–1722.
6. N.B. McKeown, Phthalocyanine materials: synthesis, structure and function; Cambridge University, 1998.
7. D. Arıcan, M. Arıcı, A.L. Uğur, Erdoğmuş, A. Koca, Effects of peripheral and nonperipheral substitution to the spectroscopic, electrochemical and spectroelectrochemical properties of metallophthalocyanines, Electrochim. Acta, 106 (2013) 541.
8. P. Zimcik, M. Miletin, J. Ponec, M. Kostka, Z. Fiedler, Synthesis and studies on photodynamic activity of new water-soluble azaphthalocyanines, J. Photochem. Photobiol. A Chem., 155 (2003) 127.
9. A. Erdoğmuş, A. Koca, U. Avciata, A. Gül, Synthesis, Characterization and Electrochemistry of New Soluble Porphyrazine Complexes Bearing Oktakis 3- Methylbutylthio Substituents, Z. Anorg. Allg. Chem., 634 (2008) 2649.
10. a) M. Arıcı, D. Arıcan, A.L. Uğur, A. Erdoğmuş, A. Koca, Electrochemical and spectroelectrochemical properties of novel lutetium(III) mono- and bisphthalocyanines, Electrochim. Acta, 113 (2013) 668. b) C. Bozoğlu, M. Arıcı, A.L. Uğur, A. Erdoğmuş, A. Koca, Electrochemical and Spectroelectrochemical Properties of methylendioxy-phenoxy-substituted Novel Lu(III) Mono- and Bis- phthalocyanines, Synth. Met., 190 (2014) 56.
11. T. Furuto, S.K. Lee, Y. Amao, K. Asai, I. Okura, Oxygen sensing system using triplet–triplet reflectance of zinc porphyrin immobilized in polymer membrane studies by laser flash photolysis, J. Photochem. Photobiol. A Chem., 132 (2000) 81.
12. A. Erdoğmuş, M. Arıcı, Novel soluble octa-substituted phthalocyanines bearing chloro and long alkyl chain containing fluorine: Synthesis, characterization and photophysical and photochemical properties, J. Fluorin. Chem., 166 (2014) 127.
13. G. Yaşa, A. Erdoğmuş, A.L. Uğur, M.K. Şener, U. Avcıata, T. Nyokong, Photophysical and photochemical properties of novel phthalocyanines bearing nonperipherally mercaptoquinoline moiety, J. Porphyr. Phthalocya., 16 (2012) 845.
14. A. Ogunsipe, D. Maree, T. Nyokong, Solvent effects on the photochemical and fluorescence properties of zinc phthalocyanine derivatives, J. Mol. Struct., 650 (2003) 131.
15. A. Erdoğmuş, T. Nyokong, Novel, soluble, FluXoro functional substituted zinc phthalocyanines; synthesis, characterization and photophysicochemical properties, Dyes Pigments, 86 (2010) 174.
16. M. Idowu, T. Nyokong, Photophysicochemical and fluorescence quenching studies of tetra- and octa-carboxy substituted silicon and germanium phthalocyanines, J. Photochem. Photobiol. A Chem., 204 (2009) 63.
17. A. Ogunsipe, T. Nyokong,Photophysical and photochemical studies of sulphonated non-transition metal phthalocyanines in aqueous and non-aqueous media, J. Photochem. Photobiol. A Chem. 173 (2005) 211.
18. B. Sezer, M.K. Sener, A. Koca, A. Erdoğmuş, U. Avciata, Synthesis, electrochemistry, spectroelectrochemistry and electrocolorimetry of phthalocyanine-anthraquinone dyes, Synth. Met., 160 (2010) 2155.
19. A.C. Beveridge, B.A. Bench, S.M. Gorun, G.J. Diebold, Evaluation of photodynamic therapy agents through transient grating measurements, J. Phys. Chem. A, 107 (2003) 5138.
20. C. Öztürk, A. Erdoğmuş, M. Durmuş, A.L. Uğur, F.A. Kılıçarslan, İ. Erden, Highly soluble 3,4-(dimetoxyphenylthio) substituted phthalocyanines: synthesis, photophysical and photochemical studies, Spectrochim. Acta A, 86 (2012) 423.
21. A. Erdoğmuş, S. Moeno, C. Litwinski, T. Nyokong, Photophysical properties of newly synthesized fluorinated zinc phthalocyanines in the presence of CdTe quantum dots and the accompanying energy transfer processes, J. Photochem. Photobiol. A Chem. 210 (2010) 200.
22. A. Erdoğmuş, M. Durmuş, A.L. Uğur, O. Avciata, U. Avciata, T. Nyokong, Synthesis, photophysic, photochemistry and fluorescence quenching studies on highly soluble substituted oxotitanium (IV) phthalocyanine complexes, Synth. Met., 160 (2010) 1868.
23. A. Lütfi Uğur, A. Erdoğmuş, A. Koca, U. Avcıata, Synthesis, spectroscopic and electrochemical and Spectroelectrochemical properties of metal free, manganese and cobalt phthalocyanines bearing peripherally octakis-4-(Thiophen-3yl)-phenoxy, Polyhedron, 29 (2010) 3310.
24. A. Erdoğmuş, A. Koca, A.L. Uğur, I. Erden, Synthesis, electrochemical and spectroelectrochemical properties of highly soluble tetra substituted phthalocyanines with [4-(Thiophen-3yl)-phenoxy], Synth. Met., 161 (2011) 1319.
25. A. Erdoğmuş, A. Ogunsipe, T. Nyokong, Synthesis, photophysics and photochemistry of novel tetra(quinoxalinyl)phthalocyaninatobzinc(II) complexes, J. Photochem. Photobiol. A: Chem., 205 (2009) 12.
26. A. Erdoğmuş, T. Nyokong, Synthesis of zinc phthalocyanine derivatives with improved photophysicochemical properties in aqueous media, J. Mol. Struct., 977 (2010) 26.
27. M. Kandaz, M.N Yarasır, A. Koca, Ö. Bekaroglu, Synthesis, characterization and electrochemistry of novel differently octasubstituted phthalocyanines, Polyhedron , 21 (2002) 255.
28. W. Spiller, H. Kliesch, D. Worhle, S. Hackbarth, B. Röder, G. Schnurpfeil, Singlet oxygen and solvents and micellar solutions J. Porphyr. Phthalocya., 2 (1998) 145.
29. Y. Zorlu, F. Dumoulin, D. Bouchu, V. Ahsen, D. Lafont, Monoglycoconjugated water-soluble phthalocyanines. Design and synthesis of potential selectively targeting PDT photosensitisers, Tetrahedron Lett., 51 (2010) 6615.
30. M. Özer, A. Altindal, M. Mustafa, Synthesis, characterization and some properties of novel bis(pentafluorophenyl)methoxyl substituted metal free and metallophthalocyanines, Polyhedron, 25 (2006) 3593.