Synthesis and Electrohemical Properties of New Tetra-2-(4-benzyloxyphenyl)ethanol Substituted Metal Free and Metallophthalocyanines

Year 2018, Issue: 2, 22 - 26, 30.06.2018

Rıza Bayrak , Ümit Demirbaş Zekeriya Bıyıklıoğlu , Hakkı Türker Akçay Halit Kantekin

Abstract

The
novel dinitrile compound (3) and peripherally tetra
2-(4-benzyloxyphenyl)ethanol substituted metal-free (4), zinc(II) (5),
cobalt(II) (6) and copper(II) (7) phthalocyanines were synthesized and
characterizated for the first time in this study. Electrochemical
characterization of metal-free and metallophthallocyanines were determined by
using cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques. Metal-free and metallophthalocyanines having
redox inactive centers (Zn⁺², Cu⁺²) showed similar Pc
based electron transfer processes. On the other hand, Co^II metal ion
behaves as redox active cations in the core of the Co- phthalocyanine.
Therefore, Co- phthalocyanine gives one metal based reduction reaction
[Co^IIPc^-2] / [Co^IPc^-2]^-1.

Keywords

Synthesis, phthalonitrile, phthalocyanine, electrochemistry

References

• 1. Leznoff, C.C., A.B.P. Lever, A.B.P., Phthalocyanines Properties and Applications, vol. 1, New York: VCH Publisher, 1989.
• 2. Parra, V., Bouvet, M., Brunet, J., Rodríguez-Méndez, M.L. and Saja, J.A., On the effect of ammonia and wet atmospheres on the conducting properties of different lutetium bisphthalocyanine thin films, Thin Solid Films, 2008, 516, 9012-9019.
• 3. Bouvet, M., Phthalocyanine-based field-effect transistors as gas sensors, Anal. Bioanal. Chem. 2006, 384, 366-373.
• 4. Leznoff, C.C. and Lever, A.B.P., Phthalocyanines Properties and Applications, vol. 3, New York: VCH Publisher, 1993.
• 5. De La Torre, G., Vazquez, P., Agullo-Lopez, F. and Torres, T., Phtahlocyanines and related compounds: organic targets for nonlinear optical applications, J. Mater. Chem. 1998, 8, 1671-1683.
• 6. Yang, F. and Forrest, S.R., Photocurrent generation in nanostructured organic solar cells, ACS Nano, 2008, 2, 1022-1032.
• 7. Forrest, S.R., Ultrathin organic films grown by organic molecular beam deposition and related techniques, Chem. Rev. 1997, 97, 1793-1896.
• 8. Bilgin, A. Ertem, B. and Gök, Y., Synthesis and characterization of new metal-free and metallophthalocyanines containin spherical or cylindrical macrotricyclic moieties, Polyhedron, 2005, 24, 1117-1124.
• 9. Leznoff, C.C. and Lever, A.B.P., Phthalocyanines Properties and Applications, vol. 2, New York, VCH Publisher, 1993.
• 10. Emmelius, M. Pawlowski, G. and Vollmann, H.W., Materials for optical data storage, Angew. Chem. Int. Edit., 1989, 28, 1445-1471.
• 11. Leznoff, C.C. and Lever, A.B.P., Phthalocyanines, Properties and Applications, vol. 4, New York, VCH Publisher, 1996.
• 12. Yılmaz, F., Özer, M., Kani, İ. and Bekaroğlu, Ö., Catalytic activity of a thermoregulated, phase-seperable Pd(II)-perfluoroalkylphthalocyanine complex in an organic/fluorous biphasic system: Hydrogenation of olefins, Catal. Lett., 2009, 1, 642-647.
• 13. Rosenthal, I., Phthalocyanines as photodynamic sensitizers, Photochem. Photobiol., 1991, 53, 589-870.
• 14. Demirbaş, Ü., Kobak, R.Z.U., Akçay, H.T., Ünlüer, D., Koca, A., Çelik, F. and Kantekin, H., Synthesis, characterization, electrochemical and spectroelectrochemical properties of novel peripherally tetra-1,2,4-triazole substituted phthalocyanines, Synthetic Metals, 2016, 215, 68-76, 2016.
• 15. Tau, P. and Nyokong, T., Electrochemical characterisation of tetra- and octa-substituted oxo(phthalocyaninato)titanium(IV) complexes, Electrochimica Acta, 2007, 52, 3641-3650.
• 16. Seven, Ö., Dindar, B. and Gültekin, B., Microwave-assisted synthesis of some metal-free phthalocyanine derivatives and a comparison with conventional methods of their synthesis, Turkish Journal of Chemistry, 2009, 33, 123-134.
• 17. Perin, D.D. and Armarego, W.L.F., Purification of laboratory chemicals, Oxford, Pergamon, 1989.
• 18. Bayrak, R., Akçay, H.T., Durmuş, M. and Değirmencioğlu, İ., Synthesis, photophysical and photochemical properties of highly soluble phthalocyanines substituted with four 3,5-dimethylpyrazole-1-methoxy groups, J. Organomet. Chem., 2011, 696, 3807-3815.
• 19. Bayrak, R., Akçay, H.T., Pişkin, M., Durmuş, M. and Değirmencioğlu, İ., Azine-bridged binuclear metallophthalocyanines functioning photophysical and photochemical-responsive, Dyes Pigments. 2012, 95, 330-337.
• 20. Değirmencioğlu, İ., Bayrak, R., Er, M. and Serbest, K., New olefiniccentred binuclear clamshell type phthalocyanines: Design, synthesis, structural characterisation, 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, 2011, 30, 1628-1636.
• 21. Bayrak, R., Karaoğlu, K., Ünver, Y., Sancak, K., Dumludağ, F. and Değirmencioğlu, İ., Synthesis, characterization, spectral and electrical properties of peripherally tetratriazole-substituted phthalocyanines and its metal complexes, J. Organomet. Chem., 2012, 712, 57-66.
• 22. Alemdar, A., Özkaya, A.R. and Bulut, M., Synthesis, spectroscopy, electrochemistry and in situ spectroelectrochemistry of partly halogenated coumarin phthalonitrile and corresponding metal-free, cobalt and zinc phthalocyanines, Polyhedron, 2009, 28, 3788-3796.
• 23. Aktaş, A., Acar, İ., Bıyıklıoğlu, Z., Saka, E.T. and Kantekin, H., Synthesis, electrochemistry of metal-free, copper, titanium phthalocyanines and investigation of catalytic activity of cobalt, iron phthalocyanines on benzyl alcohol oxidation bearing 4-{2-[3-trifluoromethyl)phenoxy]ethoxy} groups, Synthetic Metals, 2014, 198, 212-220.
• 24. Bıyıklıoğlu, Z., Çakır, V., Çakır, D. and Kantekin, H., Crown ether-substituted water soluble phthalocyanines and their aggregation, electrochemical studies, J. Organomet. Chem., 2014, 749, 18-25.
• 25. Özgül, G., Taştemel, A., Özkaya, A.R. and Bulut, M., Synthesis, characterization and comparative electrochemistry of beta and alpha tetra-[4-oxy-3-methoxybenzoic acid]-substituted Zn(II), Co(II) and Cu(II) phthalocyanines, Polyhedron, 2015, 85, 181-189.
• 26. Sevim, M., Yaraşir, M.N., Koca, A. and Kandaz, M., Novel scorpion type phthalocyanine chemosensors for detection of selective-metal ion by inducing H- and J-aggregations in solution; synthesis, characterization and electrochemistry, Dyes Pigments, 2014, 111, 190-201.
• 27. Odabaş, Z., Orman, E.B., Durmuş, M., Dumludağ, F. and Bulut, M., Novel alpha-7-oxy-4-(4-methoxyphenyl)-8-methylcoumarin substituted metal-free, Co(II) and Zn(II) phthalocyanines: Photochemistry, photophysics, conductance and electrochemistry, Dyes Pigments, 2012, 95, 540-552.
• 28. Günsel, A., Kandaz, M., Koca, A. and Salih, B., Peripheral and non-peripheral-designed multifunctional phthalocyanines; synthesis, electrochemistry, spectroelectrochemistry and metal ion binding studies, Polyhedron, 2011, 30, 1446-1455.