Tetrakis(4-bromophenoxy)phthalocyanine, its metal complexes, and their sulfonated derivatives: the synthesis and spectra
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Tetrakis(4-bromophenoxy)phthalocyanine, its metal complexes, and their sulfonated derivatives: the synthesis and spectral properties* A. S. Vashurin, T. V. Tikhomirova, A. A. Filippova, N. A. Futerman, V. E. Maizlish, and Yu. S. Marfin Ivanovo State University of Chemistry and Technology, 7 Sheremetevsky prosp., 153000 Ivanovo, Russian Federation. Fax: +7 (493) 241 7995. E-mail: [email protected] Tetrakis(4-bromophenoxy)phthalocyanine and its metal complexes (M = Mg, Co, Cu, Zn) were synthesized. Sulfochlorination of these compounds followed by hydrolysis of the sulfochlorides gave tetrakis(2-sulfo-4-bromophenoxy)phthalocyanine and corresponding sulfonated metallophthalocyanines (except M = Cu). Spectral properties of the compounds synthesized were investigated. It was shown that the introduction of sulfo groups leads to a bathochromic shift of the Q-band in the absorption spectra recorded in DMF and to a hypsochromic shift of the Q-band in the absorption spectra recorded in sulfuric acid. Key words: phthalocyanines, metal complexes, synthesis, spectroscopy.
Recently, there has been rapid progress in synthetic chemistry of tetrapyrrole macroheterocyclic compounds including various metal complexes of substituted phthalocyanines.1—4 Considerable interest in metallophthalocyanines (MPc) and their structural analogues is due to (i) intense coloration in a wide range of colors, which depends on the nature of substituents at the periphery of the macrocycle,5 and (ii) the variety of redox processes involving the molecules in question and determined by both the presence of the 18 π-electron closed conjugated system of the phthalocyanine macrocycle and the nature of the central metal cation.6,7 High chemical and thermal stability as well as other chemical and physical properties of metallophthalocyanines underlie their application as industrial dyes,8 catalysts,9,10 photoconductive polymers,11 sensors,12,13 potential photosensitizers for photodynamic therapy of cancer,14 etc. Symmetrically substituted metallophthalocyanines seem to be promising for nonlinear optical devices.15 However, phthalocyanines are of limited use because of low solubility, intermolecular aggregation that is due to π-stacking, and hydrophobic character of cores.16,17 Selfassociation makes metallophthalocyanine molecules almost photophysically inactive since the absorbed energy is scattered, which leads to a decrease in fluorescence intensity and generation of singlet oxygen that are necessary for utilizing МРс as photosensors and photosensitizers, respectively. A promising route to nonaggregated phthalocyanine-based materials (including those based on * Based on the materials of the XXI Mendeleev Congress on General and Applied Chemistry (September 9—13, 2019, St. Petersburg, Russia).
solid phthalocyanines) is to introduce in the macrocycle periphery of the bulky phenoxyl substituents (e.g., 2,6-diisopropylphenol, 2,6-diphenylphenol, and 2,6-dimethylphenol).18 To improve the photophysical and photosensitizing properties of the phthalocyanine macr
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