Newly synthesized peripherally octa-substituted zinc phthalocyanines carrying halogen terminated phenoxy-phenoxy moiety: comparative photochemical and photophysical features

This study reports the 3 new phthalonitrile derivatives, namely 4, 5 Bis-[4-(4-bromophenoxy) phenoxy] phthalonitrile (1), 4,5 Bis-[4-(4-chlorophenoxy) phenoxy]phthalonitrile (2), and 4, 5 Bis[4-(4-fluorophenoxy) phenoxy] phthalonitrile (3). Their octasubstituted zinc phthalocyanines (4, 5, 6) are reported for the first time in this study. The resulting compounds were characterized by utilizing some spectroscopic methods, such as UV-Vis, 1 HNMR, FT-IR spectroscopy, as well as mass spectraand elemental analysis. To show photosynthesizer’s potential, emission $(F_F)$, singlet oxygen $^{1}O_{2}$, and photodegradation quantum yields $Phi_DeltaPhi_d$ of octaperipherally phthalocyanines (Pcs) were performed in the solutions, such as biocompatible solvent DMSO (dimethyl sulfoxide) as well as DMF (dimethylformamide) and THF (tetrahydrofuran). Solvent and octa-peripherally binding effect of the halogen (Br, Cl,F) terminated phenoxy-phenoxy groups on phthalocyanine rings for photophysicochemical properties (4, 5, and 6) were compared with the tetra-peripherally and tetra nonperipherally substituted derivatives. The new dyes (4 to 6) may be evaluated in photodynamic therapy (PDT) of cancer as photosensitizers due to efficient $^{1}O_{2}$ from 0.55 to 0.75.

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1. Dahlen MA. The phthalocyanines a new class of synthetic pigments and dyes. Industrial & Engineering Chemistry 1939; 31: 839-847. doi: 10.1021/ie50355a012
2. Mahapatra NN. Textile Dyeing. New Delhi, India: Woodhead Publishing,, , 2018.
3. Rongrong C, Haixia L, Deryn C, Guofeng W. Unraveling oxygen reduction reaction mechanisms on carbon-supported Fe-phthalocyanine and Co-phthalocyanine catalysts in alkaline solutions. The Journal of Physical Chemistry C 2009; 113 (48): 20689-20697. doi: 10.1021/ jp906408y
4. Norman H, Stucky GD, Chadwick T. Shape selectivity in hydrocarbon oxidations using zeolite encapsulated iron phthalocyanine catalysts. Journal of the Chemical Society, Chemical Communications 1986; 20: 1521-1522. doi: 10.1039/C39860001521
5. Helen JM, Peter MB , Neil BM. Catalysis by microporous phthalocyanine and porphyrin network polymers. Journal of Materials Chemistry 2008; 18 (5): 573-578. doi: 10.1039/B715660J
6. Sezer MB, Şener K, Koca A, Erdoğmuş A, Avcıata U. Synthesis, electrochemistry, spectroelectrochemistry and electrocolorimetry of phthalocyanine-anthraquinone hybrids.Synthetic Metals Volume 2010; 160: 2155-2166. doi: 10.1016/j.synthmet.2010.08.002
7. Simon J, Sirlin C. Mesomorphic molecular materials for electronics, optoelectronics, iono-electronics: octaalkyl-phthalocyanine derivatives. Pure and Applied Chemistry 1989; 61 (9): 1625-1629. doi: 10.1351/pac198961091625
8. Gonz´alez-rodr´ıguez D, Torres T, Dirk MG, Rivera J, Herranz MÁ. Subphthalocyanines: tuneable molecular scaffolds for intramolecular electron and energy transfer processes. Journal of American Chemical Society 2004; 36 (2): 1-36. doi: 10.1021/ja039883v
9. Vogel M, Doka S, Breyer C, Lux-Steiner M, Fostiropoulos K. On the function of a bathocuproine buffer layer in organic photovoltaic cells. Applied Physics Letters 2006; 89 (16): 163501. doi: 10.1063/1.2362624
10. Peumans P, Forrest SR. Very-high-efficiency double-heterostructure copper phthalocyanine/C60 photovoltaic cells. Applied Physics Letters 2001; 79 (1): 126-128. doi: 10.1063/1.1384001
11. Raymond B. Photosensitizers of the porphyrin and phthalocyanine series for photodynamic therapy. Chemical Society Reviews 1995; 24 (1): 19-33.
12. John DS. Phthalocyanines as photosensitizers in biological systems and for the photodynamic therapy of tumors. Photochemistry and Photobiology 1986; 43 (6): 691-699. doi: 10.1039/CS9952400019
13. Michael H, Danilo D, Markus B, Sergej V. Conjugated macrocycles as active materials in nonlinear optical processes: optical limiting effect with phthalocyanines and related compounds. The Chemical Record 2002; 2 (3): 129-148. doi: 10.1002/tcr.10024
14. Keleş T, Bıyıklıoğlu Z, Gültekin E, Bekircan O. Synthesis and electrochemical properties of peripheral, nonperipheral tetra [2-(3,5-diphenyl1H-1,2,4-triazol-1-yl)ethoxy] substituted cobalt(II), manganese(III) phthalocyanines. Inorganica Chimica Acta 2019; 487: 201-207. doi: 10.1016/j.ica.2018.12.010
15. Schumann S, Hatton RA, Jones TS. Organic photovoltaic devices based on water-soluble copper phthalocyanine. The Journal of Physical Chemistry C 2011; 115 (11): 4916-4921. doi: 10.1021/jp109544m
16. John M, Martin JS. Transition assignments in the ultraviolet-visible absorption and magnetic circular dichroism spectra of phthalocyanines. Inorganic Chemistry 2001; 40 (4): 812-814. doi: 10.1021/ic0009829
17. Durmuş M, Erdoğmuş A, Ogunsipe A, Nyokong T. The synthesis and photophysicochemical behaviour of novel water-soluble cationic indium (III) phthalocyanine. Dyes and Pigments 2009; 82: 244-250. doi: 10.1016/j.dyepig.2009.01.008
18. Erdoğmuş A, Arıcı M. Novel soluble octa-substituted phthalocyanines bearing chloro and long alkyl chain containing fluorine: synthesis, characterization and photophysical and photochemical properties. Journal of Fluorine Chemistry 2014; 166: 127-133. doi: 10.1016/j. jfluchem.2014.08.005
19. Güzel E, Atmaca GY, Erdoğmus A, Burkut MK. Novel sulfonated hydrophilic indium(III) and gallium(III) phthalocyanine photosensitizers: preparation and investigation of photophysicochemical properties, Journal of Coordination Chemistry 2017; 70: 2659-2670. doi: 10.1080/00958972.2017.1366471
20. Kırbaç E, Erdoğmuş A, Atmaca GY. Novel highly soluble fluoro, chloro, bromo-phenoxy-phenoxy substituted zinc phthalocyanines: synthesis, characterization and photophysicochemical properties. Journal of Organometallic Chemistry 2014; 751: 115-122. doi: 10.1016/j. jorganchem.2013.12.005
21. Kırbaç E, Erdoğmuş A. New non-peripherally substituted zinc phthalocyanines: synthesis, and comparative photophysicochemical properties. Journal of Molecular Structure 2020; 1202: 127392. doi: 10.1016/j.molstruc.2019.127392
22. Erdoğmuş A, Nyokong T. New soluble methylendioxy-phenoxy-substituted zinc phthalocyanine derivatives: synthesis, photophysical and photochemical studies. Polyhedron 2009; 28: 2855-2862. doi: 10.1016/j.poly.2009.06.019
23. Uğur AL, Erdoğmuş A, Koca A, Avcıata U. Synthesis, spectroscopic, electrochemical and spectroelectrochemical properties of metal free, manganese, and cobalt phthalocyanines bearing peripherally octakis-[4-(thiophen-3-yl)-phenoxy] substituents. Polyhedron 2010; 29: 3310-2217. doi: 10.1016/j.poly.2010.09.008
24. Ahmetali E, Atmaca GY, Karaoğlu HP, Koçak MB, Erdoğmuş A. Photophysical and photochemical properties of newly synthesized zinc(II) and chloroindium(III) phthalocyanines substituted with 3,5-bis (trifluoromethyl)phenoxy groups. J Porphyrins Phthalocyanines 2019; 23: 960-968. doi: 10.1142/S108842461950055X
25. Korkmaz E, Ahmetali E, Atmaca GY, Karaoğlu HP, Erdoğmuş A et al. Investigation of photophysical and photochemical properties of phthalocyanines bearing fluorinated groups. Monatshefte für Chemie 2020; 151: 181-190. doi: 10.1007/s00706-019-02543-y
26. Koca B, Hamuryudan E, Catak S, Erdoğmuş A, Monari A et al. Exploring the photophysics of polyfluorinated phthalocyanine derivatives as potential theranostic agents. The Journal of Physical Chemistry C 2019; 123: 24417-24425. doi: 10.1021/acs.jpcc.9b07053
27. Nyokong T. Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines. Coordination Chemistry Reviews 2007; 251: 1707-1722. doi: 10.1016/j.ccr.2006.11.011