Ömer Faruk Öztürk, Mehmet Pişkin, Zafer Odabaş

Synthesis, spectroscopy, and photophysical properties of newly magnesium (II) phthalocyanine

2(3),9(10),16(17),23(24)-tetrakis-2,6-dimethoxyphenoxy substituted magnesium (II) phthalocyanine, which has very good solubility in polar and non-polar solvents and does not aggregate, was synthesized. Its structure was characterized by spectroscopic methods such as elemental analysis, UV-vis, FT-IR, MALDI-TOF mass and 1H NMR. It has very good solubility in polar aprotic solvents such as dimethyl sulfoxide, N, N- Dimethylformamide, tetrahydrofuran, dichloromethane, and non-polar solvents such as toluene, chloroform. Its aggregation properties have been studied both in the solvents mentioned above and in N, N- Dimethylformamide at different concentrations. Its photophysical properties were determined in N, N-dimethyl formamide. The effects of the nature and presence of 2,6-dimethoxyphenoxy group, which is an antioxidant derivative, on the phthalocyanine skeleton on the spectroscopic and photophysical properties were investigated by comparing it with unsubstituted magnesium (II) phthalocyanine. It can be a good nominee for various technological applications in that it does not aggregate and has good solubility in polar and non-polar solvents, as well as better and favorable fluorescence properties than its analog in the previous study.

PDF

___

[1]. Ingram D.J.E., Bennett J.E., “Paramagnetic resonance in phthalocyanine, chlorophyll, and hemoglobin derivatives”, The Journal of Chemical Physics, 22(6), (1954), 1136-1137.
[2]. Tian M., Wada T., Kimura-Sudab H., Sasabea H., “Novel non-aggregated unsymmetrical metallophthalocyanines for second-order non-linear optics”, Materials Chemistry Communication, 7(6), (1997), 861-863.
[3]. Sorokin A.B., “Phthalocyanine metal complexes in catalysis”, Chemical Reviews, 113(10), (2013), 8152- 8191.
[4]. Ben-Hur E., Rosenthal I., “Photosensitized inactivation of Chinese hamster cells by phthalocyanines”, Photochemistry and Photobiology, 42(2), (1985), 129— 133.
[5]. Bayrak R., Albay C., Koç M., Altın İ., Değirmencioğlu İ., Sökmen M., “Preparation of phthalocyanine/TiO2 nanocomposites for photocatalytic removal of toxic Cr(VI) ions Process”, Process Safety and Environmental Protection, 102, (2016), 294-302.
[6]. Petritsch K., Friend R.H., Lux A., Rozenberg G., Moratti S.C., Holmes A.B., “Liquid Crystalline Phthalocyanines in Organic Solar Cells”, Synthetic Metals, 102, (1999), 1776-1777.
[7]. Lü K., Zhou J., Zhou L., Chen X.S., Chan S.H., Sun Q., “Pre-combustion CO2 capture by transition metal ions embedded in phthalocyanine sheets”, The Journal of Chemical Physics, 136(23), (2012), 234703.
[8]. Singh S., Aggarwal A., Bhupathiraju N. V. S. Dinesh K., Arianna G., Tiwari K., Drain C.M., “Glycosylated Porphyrins, Phthalocyanines, and Other Porphyrinoids for Diagnostics and Therapeutics”, Chemical Reviews, 115(118), (2015), 10261−10306.
[9]. Snow A.W., The Porphyrin Handbook Phthalocyanines: Properties and Materials in Phthalocyanine Aggregation, Vol.17, K.M. Kadish, K.M. Smith, R. Guilard Eds. New York, Academic Press, 2003, 129-176.
[10]. Lukyanets E.A., Nemykin V.N., “The key role of peripheral substituents in the chemistry of phthalocyanines and their analogs”, Journal of Porphyrins and Phthalocyanines, 14(01), (2010), 1-40.
[11]. Qi Z-L., Cheng Y-H., Xu Z., Chen M-L, “Recent Advances in Porphyrin-Based Materials for Metal Ions Detection”, International Journal of Molecular Science 21, (2020), 5839- 5866.
[12]. Ishii K., Kobayashi N., in The Porphyrin Handbook, ed. K. M. Kadish, K. M. Smith, R. Guiard, Academic Press, New York, 2003, vol. 16, pp.1–42.
[13]. Janczak J., Kubiak R., “From 1,3-dicyanobenzene to 3- cyanobenzamide—its molecular structure in the gasphase and in the crystal”, Journal of Molecular Structure, 644 (2003), 13-21.
[14]. Janczak J., Śledź M., Kubiak R., “Catalytic trimerization of 2- and 4-cyanopyridine isomers to the triazine derivatives in presence of magnesium phthalocyanine”, Journal of Molecular Structure, 659, (2003), 71-79.
[15]. McKewon N.B., “Phthalocyanine Materials: Synthesis, Structure and Function”, Cambridge University Press, Cambridge, 1998.
[16]. Loutfy, R.O., Hor, A.M., DiPaola-Baranyi, G., Hsiao, C.K. “Electrophotographic Photoreceptors Incorporating Aggregated Phthalocyanines”, Journal of Imaging Science, 29(3), (1985), 116-121.
[17]. Khe N.C., Aizawa M., Kaishi N.K., “The Use of Magnesium Phthalocyanine Compound as Electrophotographic Receptor Available for Laser Diode Recording”, 1986(3), (1986), 393- 401.
[18]. Herbst W., Hunger K., Industrial Organic Pigments: Production, Properties, Applications, Wiley-VCH, New York, 1993.
[19]. Loutfy R.O., McIntre L.F., “Photoelectrochemical solar energy conversion by polycrystalline films of phthalocyanine” Solar Energy Materials, 6(4), (1982), 467-479.
[20]. Loutfy R.O.,“High-conversion polymerization of fluorescence probes. 1. Polymerization of methyl methacrylate”, Macromolecules, 14, (1981), 270-275.
[21]. Ghosh A.K., Morel D.L., Feng T., Shaw R.F., Rowe C.A., “Photovoltaic and rectification properties of Al/Mg phthalocyanine/Ag Schottky‐barrier cells”, Journal of Applied Physics, 45, (1974), 230-236.
[22]. Bayona A.M.D.P., Mroz P., Thunshelle C., Hamblin M.R., Design features for optimization of tetrapyrrole macrocycles as antimicrobial and anticancer photosensitizers, Chemical Biology & Drug Design, 89(2), (2017), 192-206.
[23]. Soares A.R.M. , Tomé J.P.C. , Neves M.G.P.M.S., Tomé A.C., Cavaleiro J.A.S. , Torres T., “Synthesis of water-soluble phthalocyanines bearing four or eight dgalactose units”, Carbohydrate Research, 344(4), (2009), 507-510.
[24]. Kandaz M. , Özkaya A.R., Koca A., Salih B., “Water and alcohol-soluble octakis-metalloporphyrazines bearing sulfanyl polyetherol substituents: synthesis, spectroscopy, and electrochemistry”, Dyes and Pigments, 74(2), (2007), 483-489.
[25]. Nishida M., Horiuchi H., Momotake A., Nishimura Y., Hiratsuka H., Arai T., “Singlet molecular oxygen generation by water-soluble phthalocyanine dendrimers with different aggregation behavior”, Journal of Porphyrins and Phthalocyanines, 15, (2011), 47-53.
[26]. Janczak J., Idemori Y.M., “Synthesis, crystal structure and characterisation of aquamagnesium phthalocyanine—MgPc(H2O). The origin of an intense near-IR absorption of magnesium phthalocyanine known as ‘X-phase’ ”, Polyhedron, 22(9), (2003), 1167-1181.
[27]. Taştemel A., Karaca B.Y., Durmuş M., Bulut M., “Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(mmethoxyphenyl) coumarin groups”, Journal of Luminescence, 168, (2015), 163–171.
[28]. Pişkin Mehmet, “The novel 2,6-dimethoxyphenoxy substituted phthalocyanine dyes having high singlet oxygen quantum yields”, Polyhedron, 104, (2016), 17- 24.
[29]. Pişkin M., Öztürk Ö.F., Odabaş Z. “Determination of photophysical, photochemical and spectroscopic properties of novel lead(II) phthalocyanines”, Polyhedron, 182, (2020), 114480.
[30]. Pişkin M., Öztürk Ö.F., Odabaş Z., "Newly Soluble and Non-Aggregated Copper(II) and Tin(II) Phthalocyanines: Synthesis, Characterization and Investigation of Photophysical and PhotochemicalResponsive", Karaelmas Science and Engineering Journal, 7 (2), (2017), 627-637.
[31]. Pişkin M., Odabaş Z., "Synthesis, Characterization and Spectroscopic Properties of Novel Mono-Lutetium(III) Phthalocyanines", Karaelmas Science and Engineering Journal, 6 (2), (2016), 307-314.
[32]. Pişkin M., Can N., Odabaş Z., Altındal A., "Toluene vapor sensing characteristics of novel copper(II), indium(III),mono-lutetium(III) and tin(IV) phthalocyanines substituted with 2,6- dimethoxyphenoxy bioactive moieties", Journal of Porphyrins and Phthalocyanines, 22, (2018), 1–9.
[33]. [33] Kharisov B.I., Blanco L.M., Torres-Martinez L.M., García-Luna A., “Electrosynthesis of Phthalocyanines: Influence of Solvent”, Industrial & Engineering Chemistry Research, 38(8) (1999) 2880-2887.
[34]. Stillman M.J., Nyokong T., Phthalocyanines Properties and Applications, vol. 1, C. C. Leznoff and A. B. P Lever, Eds., New York, Wiley-VCH Publishers,1989, ch. 3, pp. 133–289.
[35]. Enkelkamp H., Nolte R.J.M.,” Molecular materials based on crown ether functionalized phthalocyanines”, Journal of Porphyrins and Phthalocyanines, 4(5), (2000), 454-459.
[36]. Dominquez D.D., Snow A.W., Shirk J.S., Pong R.G.S., “Polyethyleneoxide‐capped phthalocyanines: limiting phthalocyanine aggregation to dimer formation”, Journal of Porphyrins and Phthalocyanines, 5(7), (2001), 582-592.
[37]. Nyokong T.,“Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines”, Coordination Chemistry Reviews, 251(13-14), (2007), 1707-1722.
[38]. Tuhl A., Chidawanayika W., Ibrahim H. M., Al-Awadi N., Litwinski C., Nyokong T., Behbehani H., Manaa H., Makhseed S., “Tetra and octa(2,6-di-isopropylphenoxy)-substituted phthalocyanines: a comparative study among their photophysicochemical properties”, Journal of Porphyrins and Phthalocyanines, 16(01), (2012), 163-174.
[39]. Kobayashi N., Ogata H., Nonaka N., Luk'yanets E.A., “Effect of Peripheral Substitution on the Electronic Absorption and Fluorescence Spectra of Metal‐Free and Zinc Phthalocyanines”, Chemistry—A European Journal, 9(20), (2003), 5123-5134.
[40]. Çapkın A., Pişkin M., Durmuş M., Bulut M., “Spectroscopic, photophysical and photochemical properties of newly metallo-phthalocyanines containing coumarin derivative”, Journal of Molecular Structure,1213, (2020), 128145.
[41]. Akçay H.T., Pişkin M., Demirbaş Ü., Bayrak R., Durmuş M., Menteşe E., Kantekin H., “Novel triazole bearing zinc(II) and magnesium(II) metallophthalocyanines: Synthesis, characterization, photophysical and photochemical properties”, Journal of Organometallic Chemistry, 745 (746), (2013), 379- 386.
[42]. Kantekin H., Yalazan H., Kahriman N., Ertem B., Serdaroğlu V., Pişkin M., Durmuş M.,“New peripherally and non-peripherally tetra-substituted metal-free, magnesium(II) and zinc(II) phthalocyanine derivatives fused chalcone units: Design, synthesis, spectroscopic characterization, photochemistry and photophysics”, Journal of Photochemistry and Photobiology A: Chemistry, 361, (2018), 1-11.
[43]. Mutlu F., Pişkin M., Canpolat E., Öztürk Ö.F., "The new zinc(II) phthalocyanine directly conjugated with 4- butylmorpholine units: Synthesis, characterization, thermal, spectroscopic and photophysical properties", Journal of Molecular Structure, 1201, (2020), 127169.
[44]. Şahal H., Pişkin, M., Organ G.A., Öztürk Ö.F., Kaya M., Canpolat E., "Zinc(II) phthalocyanine containing Schiff base containing sulfonamide: synthesis, characterization, photophysical, and photochemical properties" J. Coord. Chem. 71 (22), (2018), 3763– 3775
[45]. Demirbaş Ü., Pişkin M., Bayrak R., Durmuş M., Kantekin H. "Zinc(II) and lead(II) phthalocyanines bearing thiadiazole substituents: Synthesis, characterization, photophysical and photochemical properties", Journal of Molecular Structure, 1197, (2019) 594-602
[46]. Pişkin M., Canpolat E., Öztürk Ö.F. "The new zinc phthalocyanine having high singlet oxygen quantum yield substituted with new benzenesulfonamide derivative groups containing schiff base", Journal of Molecular Structure, 1202, (2020), 127181 .
[47]. Pişkin M., Öztürk Ö.F., Odabaş Z., "The photophysicochemical properties of peripherally and non-peripherally tetrakis-substituted lutetium(III) acetate phthalocyanines" Journal of Anatolian Chemistry and Chemical Education Research, 1(1), (2017), 1-12.