Yeni İyi Çözünür ve Agregasyon Yapmayan Bakır II ve Kalay II MetallibFtalosiyaninler: Sentez, Karakterizasyon ve Fotofiziksel ve Fotokimyasal Duyarlılığın Araştırılması

Yıl 2017, Cilt: 7 Sayı: 2, 627 - 637, 01.06.2017

Mehmet Pişkin , Ömer Faruk Öztürk Zafer Odabaş

Öz

Bu çalışma, non-periferal alfa- ve periferal beta- pozisyonlarda 2,6-dimetoksi gruplarıyla sübstitüe edilen agrege olmayan oldukça çözünür bakır II ve kalay II metalli ftalosiyanin bileşiklerinin sentezini ve karakterizasyonunu sunar. Bu ftalosiyaninler bilinen spektroskopik tekniklerle karakterize edilmiştir. Dimetilsülfoksit, dimetilformamit, tetrahidrofuran, toluen, asetonitril, kloroform ve diklorometan gibi bilinen organik çözücülerde mükemmel çözünürlük ve agregasyon yapamayan türler göstermiştir. Orijinal ftalosiyanin bileşiklerinin yüksek çözünürlük özellikleri ve agregasyon yapmayan türler içermesi onları bilim ve teknolojinin farklı alanlarında pek çok uygulamalarda kullanılmaları amacıyla aday yapar. Bu orjinal ftalosiyaninlerin spektroskopik özellikleri hakkında üstte bahsedilen farklı çözeltilerde ftalosiyanin merkezindeki farklı metal iyonlarının ve ftalosiyanin iskeleti üzerinde sübstitüentin pozisyon etkileri ve agregasyon özellikleri belirlenmiştir. Ayrıca, bileşiklerin dimetilsülfokit çözeltisinde farklı konsantrasyonlardaki agregasyon özellikleri de incelenmiştir. Yeni sentezlenen bakır metalli ftalosiyaninler, ftalosiyanin çekirdeğinde merkez metalinin paramagnetik davranışı ve geçiş metalinden dolayı floresans, fotofiziksel ve fotokimyasal özellikleri değerlendirilmedi. Alfa ve betasübstitüentli kalay II metalli orijinal ftalosiyanin bileşiklerinin fotofiziksel floresans kuantum verimleri ve ömürleri ve fotokimyasal özellikleri singlet oksijen kuantum verimleri, fotobozunma kuantum verimleri hakkında ftalosiyanin iskeleti üzerindeki sübstitüent ve sübstitüentin pozisyonlarının etkileri de ilk defa bu çalışmada incelenmiş ve rapor edilmiştir

Anahtar Kelimeler

Bakır II, Agregasyon yapmayan, Fotokimyasal, Fotofiziksel, Ftalosiyanin, Çözünür, Kalay II

Newly ideal soluble and non-aggregated copper II and tin II metallo phthalocyanines: Synthesis, characterization and investigation of photophysical and photochemical-responsive

Öz

This work presents the synthesis and characterization of non-aggregated and highly soluble copper II and tin II phthalocyanines substituted with 2,6-dimethoxyphenoxy groups at the non-peripheral alpha and peripheral beta positions. The phthalocyanines have been characterized by common spectroscopic techniques. They show excellent solubility and non-aggregated species in common organic solvents such as dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, acetonitrile, chloroform, dichloromethane, which makes them candidates to use for many applications in different fields of science and technology. The effects positions of substituent and aggregation on the phthalocyanine skeleton and the variety of central metal ions on the phthalocyanine core on their spectroscopic properties of the novel phthalocyanines were determined in different solvents as mentioned above. The novel synthesized copper phthalocyanines were not evaluated for fluorescence, photophysical and photochemical properties due to transition metal and paramagnetic behavior of central metal in the phthalocyanine cavity. The effects of substituent and their position on the phthalocyanine skeleton on the tin II phthalocyanines’s photophysical fluorescence quantum yields and lifetimes and photochemical properties singlet oxygen generation and photodegradation under light irradiation were also investigated in dimethylsulfoxide for the first time. The obtained results for tin II phthalocyanines were also compared with unsubstituted zinc II phthalocyanine for determination of substitution effect and central metal effect on photophysical and photochemical properties in dimethylsulfoxide.

Anahtar Kelimeler

Copper II, tin II, phthalocyanine, soluble, non-aggregated, photochemical, photophysical.

Kaynakça

• Leznoff, CC., Lever, AbP. 1989. Phthalocyanines, Properties and Applications Vol.1, Wiley–VCH, New York, pp-341–392.
• Leznoff, CC., Lever, AbP. 1993. Phthalocyanines, Properties and Applications Vol.3, Wiley–VCH, New York, pp-119–167.
• Leznoff, CC., Lever, AbP. 1996. Phthalocyanines, Properties and Applications Vol.4, Wiley–VCH, New York, pp-79–181.
• Ince, M., Martínez-Díaz, MV. barber, J., Torres, T. 2011. Liquid Crystalline Phthalocyanine-Fullerene Dyads. J. Mater. Chem., 21: 1531-1536.
• Cicoira, F., Coppede, N., Iannotta, S., Martel, R. 2011. Ambipolar copper phthalocyanine transistors with carbon nanotube array electrodes. Appl. Phys. Lett., 98 (18): 183303- 183305.
• bohrer, FI., Sharoni, A., Colesniuc, C., Park, J., Schuller, IK., Kummel, AC., Trogler, WC. 2007. Gas sensing mechanism in chemiresistive cobalt and metal-free phthalocyanine thin films. J. Am. Chem. Soc, 129 (17): 5640-5646.
• Nagel, S., Lener, M., Keil, C., Gerdes, R., Lapok, L., Gorun, S.M., Schlettwein, D. 2011. Electrochromic switching of evaporated thin films of bulky, electronic deficient metallo- phthalocyanines. J. Phys. Chem. C., 115: 8759-8767.
• Shirk, JS., Pong, RGS., Flom, SR., Heckmann, H., Hanack, M. 2000. Effect of axial substitution on the optical limiting properties of indium phthalocyanines. J. Phys. Chem. A., 104: 1438-1449.
• Şahin, S., Altun, S., Altındal, A., Odabaş, Z. 2015. Synthesis of novel azo-bridged phthalocyanines and their toluene vapour sensing properties. Sens. Actuators, B., 206: 601-608.
• Durmuş, M., Nyokong, T. 2007. The synthesis, fluorescence behaviour and singlet oxygen studies of new water-soluble cationic gallium (III) phthalocyanines. Inorg. Chem. Commun., 10: 332-338.
• Tekdaş, DA., Durmuş, M., Yanık, H., Ahsen, V. 2012. Photodynamic therapy potential of thiol-stabilized CdTe quantum dot-group 3A phthalocyanine conjugates (QD-Pc). Spectrochim. Acta A., 93: 313-320.
• The values of singlet oxygen quantum yield ranging from
• Jiang XJ., Huang JD., Zhu YJ., Tang FX., Ng DKP., Sun JC. 2006. Preparation and in vitro photodynamic activities of novel axially substituted silicon (IV) phthalocyanines and their bovine serum albumin conjugates. Bioorg. Med. Chem. Lett., 16: 2450-2453.
• Pişkin, M., Durmuş, M., bulut, M. 2011. Synthesis, characterization, photophysical and photochemical properties of 7-oxy-3-methyl-4-phenylcoumarin-substituted indium phthalocyanine. Spectrochim. Acta A., 373: 107-116.
• Alamin Ali, HE., Pişkin, M., Altun, S., Durmuş, M., Odabaş, Z. 2016. Synthesis, characterization, photophysical, and photochemical properties of novel zinc(II) and indium(III) phthalocyanines containing 2-phenylphenoxy units. J. Lumin., 173: 113-119.
• Pişkin, M., Durmuş, M., bulut, M. 2011. Highly soluble 7-oxy-3-(4-methoxyphenyl) coumarin bearing zinc phthalocyanines: Synthesis and investigation of photophysical and photochemical properties. J. Photochem. Photobiol. A., 223: 37-49.
• Akçay, HT., Pişkin, M., Demirbaş, Ü., bayrak, R., Durmuş, M., Menteşe, E., Kantekin, H. 2013. Novel triazole bearing zinc(II) and magnesium(II) metallo-phthalocyanines: Synthe- sis, characterization, photophysical and photochemical prop- erties, J. Organomet. Chem. 2013, 745(746): 379-386.
• Nas, A., Demirbaş, Ü., Pişkin, M., Durmuş, M., Kantekin, H. 2014. The photophysical and photochemical properties of new unmetallated and metallated phthalocyanines bearing four 5-chloroquinolin-8-yloxy substituents on peripheral sites. J. Lumin., 145: 635-642.
• Demirbaş, Ü., bayrak, R., Pişkin, M., Akçay, H.T., Durmuş, M., Kantekin, H. 2013. Synthesis, photophysical and photochemical properties of novel tetra substituted metal free and metallophthalocyanines bearing triazine units. J. Organomet. Chem., 724: 225-234.
• Aktaş, A., Pişkin, M., Durmuş, M., bıyıklıoğlu, Z. 2014. Synthesis, photophysical and photochemical properties of zinc phthalocyanines bearing fluoro-functionalized substituents. J. Lumin., 145: 899-906.
• Pişkin, M. 2016. The novel 2,6-dimethoxyphenoxy substituted phthalocyanine dyes having high singlet oxygen quantum yields. Polyhedron, 104: 17-24.
• Kulaç, D., bulut, M., Altındal, A., Özkaya, AR., Salih, b., bekaroğlu, Ö. 2007. Synthesis and characterization of novel 4-nitro-2-(octyloxy)phenoxy substituted symmetrical and unsymmetrical Zn(II), Co(II) and Lu(III) phthalocyanines. Polyhedron, 26: 5432-5440.
• bayrak, R., Akçay, HT., Pişkin, M., Durmuş, M., Değirmencioğlu, İ. 2012. Azine-bridged binuclear metallophthalocyanines functioning photophysical and photochemical-responsive. Dyes Pigm., 2012; 95: 330-337.
• Dyes Pigm., 99: 185-191.
• Kobayashi, N., Fukuda, T., Ueno, K., Ogino, H. 2001. Extremely Non-Planar Phthalocyanines with Saddle or Helical Conformation: Synthesis and Structural Characterizations. J. Am. Chem. Soc., 123: 10740–10741.
• Gürel, E., Pişkin, M., Altun, S., Odabaş, Z., Durmuş, M. 2016. The novel mesityloxy substituted metallo-phthalocyanine dyes with long fluorescence lifetimes and high singlet oxygen quantum yields. J. Photochem. Photobiol. A., 315: 42–51.
• Stillman, MJ., Nyokong T. 1989. Phthalocyanines: Properties and Applications, vol. 1, Wiley -VCH Publishers, New York, (Chapter 3). pp-222–232.
• Nyokong, T. 2007. Effects of substituents on the photochemical and photophysical properties of main group metal phthalocya- nines. Coord. Chem. Rev., 251: 1707-1722.
• Idowu, M., Nyokong, T. 2008. Synthesis, photophysics and photochemistry of tin(IV) phthalocyanine derivatives. J. Photochem. Photobiol. A., 199: 282–290.
• Moeno, S., Nyokong, T. 2009. Solvent and central metal effects on the photophysical and photochemical properties of peripherally tetra mercaptopyridine substituted metallophthalocyanines. J. Photochem. Photobiol. A., 203: 204–210.
• Mack, J., Kobayashi, N. 2011. Low Symmetry Phthalocyanines and Their Analogues. Chem. Rev. 111: 281-321.