Yeni periferal tetra-(E)-4-(3-(3-(2,4,6-trimetoksifenil)akriloil)fenoksi) substitüe metalsiz ve metalli ftalosiyaninlerin sentezi ve karakterizasyonu

Year 2021, , 189 - 197, 15.01.2021

Volkan Çakır

https://doi.org/10.17714/gumusfenbil.716981

Abstract

Bu çalışma kapsamında, yeni hidroksil bileşiği 1, ftalonitril bileşiği 3, periferal tetra-(E)-4-(3-(3-(2,4,6-trimetoksifenil)akriloil)fenoksi) substitue metalsiz (H2Pc 4) ve metalli ftalosiyaninlerin (Co(II)Pc 5, Cu(II)Pc 6, Ni(II)Pc 7, Zn(II)Pc 8) sentezi ve karakterizasyonu gerçekleştirilmiştir. 3 Bileşiğinin siklotetramerizasyon reaksiyonu sonucu yeni periferal tetra substitue metalsiz ftalosiyanin (4) elde edilmiştir. Yeni periferal tetra substitue metalli ftalosiyaninler (Co(II)Pc 5, Cu(II)Pc 6, Ni(II)Pc 7, Zn(II)Pc 8) ise 3 bileşiğinin n-pentanol ve 1,8-diazabisiklo[5.4.0]undek-7-en (DBU) karışımı içerisinde sırası ile susuz CoCl2, CuCl2, NiCl2 ve Zn(CH3COO)2 tuzları ile kaynatılması sonucu sentezlenmiştir. Elde edilen yeni ftalosiyanin kompleksleri kloroform, diklorometan, tetrahidrofuran, dimetilsülfoksit ve dimetilformamid gibi yaygın organik çözücüler içerisinde iyi çözünürlük göstermiştir. Sentezi gerçekleştirilen yeni bileşikler (1, 3, 4, 5, 6, 7 ve 8) IR, 1H NMR, 13C NMR, kütle, UV-Vis spektroskopi ve elementel analiz teknikleri kullanılarak karakterize edilmiştir.

Keywords

Ftalosiyanin, Karakterizasyon, Periferal, Sentez, Siklotetramerizasyon

Synthesis and characterization of novel peripherally tetra-(E)-4-(3-(3-(2,4,6-trimethoxyphenyl)acryloyl)phenoxy) substituted metal-free and metallophthalocyanines

Abstract

In this study, a new hydroxyl derivate 1, phthalonitrile derivative 3 and peripherally tetra-(E)-4-(3-(3-(2,4,6-trimethoxyphenyl)acryloyl)phenoxy) substituted new metal-free 4, Co(II) 5, Cu(II) 6, Ni(II) 7 and Zn(II) 8 phthalocyanine derivatives were synthesized and characterized. Metal-free Pc 4 was prepared by cyclotetramerization of phthalonitrile derivate 3 and MPcs 5–8 were synthesized by heating 3 with CoCl2, CuCl2, NiCl2 and Zn(CH3COO)2 in n-pentanol in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), respectively. These phthalocyanines were good soluble in organic solvents such as chloroform,
dichloromethane, tetrahydrofuran, dimethylsulfoxide and dimethylformamide. The new compounds (1, 3, 4, 5, 6, 7 and 8) were characterized by a combination of IR, 1H NMR, 13C NMR, mass, UV-Vis spectroscopy and elemental analysis techniques.

Keywords

Phthalocyanine, Characterization, Peripheral, Synthesis, Cyclotetramerization

References

• Ao, R., Kümmerl, L. ve Haarer, D. (1995). Present limits of data storage using dye molecules in solid matrices. Advanced Materials, 7, 495-499, https://doi.org/10.1002/adma.19950070522
• Bekaroğlu, Ö. (1996). Phthalocyanines containing macrocycles applied. Organometallic Chemistry, 10, 605-622, https://doi.org/10.1002/(SICI)1099-0739(199610)10:8<605::AID-AOC527>3.0.CO;2-U
• Değirmencioğlu, İ., Bayrak, R., Akcay, H. T., Pişkin, M. ve Durmuş, M. (2012). Azine-bridged binuclear metallophthalocyanines functioning photophysical and photochemical-responsive. Dyes and Pigments, 95, 330-337, https://doi.org/10.1016/j.dyepig.2012.05.010
• Değirmencioğlu, İ., Bayrak, R., Er, M. ve Serbest, K. (2011). New olefinic centred binuclear clamshell type phthalocyanines: design, synthesis, structural characterization, the stability and the change in the electron cloud at olefine-based symmetrical diphthalonitrile fragment by the combined application of UV-Vis electronic structure and theoretical methods. Polyhedron, 30, 1628-1636, https://doi.org/10.1016/j.poly.2011.03.039
• Dini, D., Barthel, M., Schneider, T., Ottmar, M., Verma, S. ve Hanack, M. (2003). Phthalocyanines and related compounds as switchable materials upon strong irradiation: the molecular engineering behind the optical limiting effect. Solid State Ionics, 165, 289–303, https://doi.org/10.1016/j.ssi.2003.08.046
• Göksoy, B., Orman, E. B., Kuruca, H., Bulut, M., Durmuş, M. ve Özkaya A. R. (2016). Mono and double decker lutetium phthalocyanines bearing iodine groups electrochemical and electrochromic properties. Journal of the Electrochemical Society, 163, 927-936, https://doi.org/10.1149/2.0421610jes
• Kluson, P., Drobek, M., Kalaji, A., Zarubova, S., Krysa, J. ve Rakusan, J. (2008). Singlet oxygen photogeneration efficiencies of a series of phthalocyanines in well-define d spectral regions. Journal of Photochemistry and Photobiology A: Chemistry, 199, 267–273, https://doi.org/10.1016/j.jphotochem.2008.06.003
• Kobayashi, N., Muranaka, A. ve Ishii, K. (2000). Symmetry-lowering of the phthalocyanine chromophore by a C2 type axial ligand. Inorganic Chemistry, 39, 2256-2257, https://doi.org/10.1021/ic9914950
• Mack, J. ve Stillman, M. J. (2001). Assignment of the optical spectra of metal phthalocyanines through spectral band deconvolution analysis and zındo calculations. Coordination Chemistry Reviews, 219-221, 993-1032, https://doi.org/10.1016/S0010-8545(01)00394-0
• Mutlu, F., Pişkin, M., Canpolat, E. ve Öztürk, Ö. F. (2020). The new zinc(II) phthalocyanine directly conjugated with 4-butylmorpholine units: synthesis, characterization, thermal, spectroscopic and photophysical properties. Journal of Molecular Structure, 1201, 127169, https://doi.org/10.1016/j.molstruc.2019.127169
• Sarkı, G., Kantekin, H., Yalazan, H., Kahriman, N., Bıyıklıoğlu, Z. ve Serdaroğlu, V. (2019). Synthesis, characterization and electrochemical studies of metal-free and metallophthalocyanines containing two different chalcone units substituted on peripherally positions. Journal of Molecular Structure, 1196, 592-603. https://doi.org/10.1016/j.molstruc.2019.05.123
• Ünlü, S., Yaraşır, M. N., Kandaz, M., Koca, A. ve Salih, B. (2008). Synthesis, spectroscopy and electrochemical properties of highly soluble fluoro containing phthalocyanines. Polyhedron, 27, 2805-2810, https://doi.org/10.1016/j.poly.2008.05.036
• Yongde, Y. ve Zhenguo, J. (2006). Improved photoreceptor decay characteristics of vanadyl-phthalocyanine films annealed under magnetic field. Journal of Photochemistry and Photobiology A: Chemistry, 179, 348–350, https://doi.org/10.1016/j.jphotochem.2005.09.005