Peripherally tetra-benzimidazole units-substituted zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysical and photochemical properties (original) (raw)
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Journal of Molecular Structure, 2017
In this study, novel phthalonitrile compounds bearing 2-methylbenzo[d]thiazol-5-yloxy groups (4 and 5) and their peripherally and non-peripherally tetra-substituted metal-free (6 and 7), zinc (II) (8 and 9), and lead (II) (10 and 11) phthalocyanine derivatives were synthesized and characterized for the first time. These novel compounds showed extremely good solubility in most common organic solvents. The novel phthalocyanine compounds presented excellent results from photophysical and photochemical examinations in DMF solution. Especially, the singlet oxygen quantum yield (F D) values of the substituted zinc (II) phthalocyanines indicate that these compounds have significant potential as photosensitizers in cancer treatment by the photodynamic therapy (PDT) technique. The fluorescence quenching behaviour of these novel phthalocyanine compounds by 1,4-benzoquinone (BQ) was also examined in DMF solution.
The facile synthesis and characterization of tetraimido-substituted zinc phthalocyanines
Dyes and Pigments, 2008
Peripherally tetraimido-substituted zinc phthalocyanines were synthesized by the reaction of tetraamino-substituted zinc phthalocyanine with maleic anhydride, phthalic anhydride and tetrachlorophthalic acid, respectively. The compounds were characterized by MS, 1 H NMR, UVevis, IR and elemental analysis, the results of which were consistent with the proposed structures. UVevis spectra showed that the wavelengths of the Q bands followed the order: Q 2c > Q 2b > Q 2a ; the strengths of the Q bands varied inversely with temperature. The compounds were stable in acid but unstable in alkali.
The synthesis and photochemical properties of peripherally and non-peripherally 1,3-bis[3-(dimethylamino)phenoxy]prop-2-oxy tetra-substituted zinc phthalocyanines (2a and 3a) and their quaternized derivatives (2b and 3b) were reported in this study. Photochemical properties of quaternized ionic zinc (II) phthalocyanines (2b and 3b) were investigated in both dimethyl sulfoxide (DMSO) and aqueous solutions, while non ionic derivatives were only studied in DMSO. The quaternized compounds exhibit excellent solubility in water, making them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. This study also showed that the water-soluble quaternized Zn(II) phthalocyanines strongly bind to blood plasma proteins such as bovine serum albumin (BSA). On the other hand, the interactions of the novel water soluble phthalocyaines with DNA were also examined.
Photophysical properties of a newly synthesized unsymmetrically substituted zinc phthalocyanine
Journal of the Turkish Chemical Society, Section A: Chemistry, 2021
A novel unsymmetrically substituted zinc phthalocyanine (ZnPc) containing six hexylthio units and a morpholinoethoxy group was synthesized and characterized. Statistical condensation reaction of two different phthalonitriles was used for the preparation of unsymmetrical ZnPc. The novel compound was purified using chromatographic methods with the help of high solubility differences of phthalonitrile derivatives. Characterization of the compound was achieved by using NMR, FT-IR, UV-Vis, and mass spectroscopic methods. The photophysical measurements were made in tetrahydrofuran (THF). Fluorescent quantum yield (ΦF) and fluorescence lifetime (τF) of unsymmetrical ZnPc were determined. Fluorescent quenching experiments were done by adding benzoquinone (BQ) in THF, and Stern-Volmer constant (Ksv) and quenching constant (kq) values were calculated.
European Journal of Medicinal Chemistry, 2011
The synthesis and photophysical parameters of two novel isosteric cationic zinc(II) phthalocyanines: 2,9(10),16(17),23(24)-tetrakis[(N-butyl-N-methylammoniumethylsulfanyl]phthalocyaninatozinc(II) tetraiodide (6) and 2,9(10),16(17),23(24)-tetrakis[(N-dibutyl-N-methylammonium)ethoxy]phthalocyaninatozinc(II) tetraiodide (7) were investigated. Maximum absorption values were 686.5 nm and 678 nm for 6 and 7, respectively, whereas singlet molecular oxygen generation was 0.42 and 0.67, respectively. The photodynamic effect and the cellular uptake of both phthalocyanines were evaluated on human nasopharynx KB carcinoma cells. After light exposure, phthalocyanine 6 showed a higher cytotoxic activity than 7. In addition, a higher intracellular uptake of 6 and a preferential localization within lysosomes were demonstrated. The production of a greater amount of reactive oxygen species after phthalocyanine 6 irradiation would be responsible for its potent phototoxic action on KB cells.
Synthesis, photophysical and photochemical studies on long chain zinc phthalocyanine derivatives
Synthetic Metals, 2008
The synthesis and characterization of 2,9,16,23-chloro-3,10,17,24-triethyleneoxysulphanylphthalocyaninato zinc(II) (CTESZnPc) is described. The photophysics and photochemistry of CTESZnPc and those of tetrakis(triethyleneoxysulphanyl)zinc phthalocyanine (TTESZnPc) and octakis-(triethyleneoxysulphanyl)zinc phthalocyanine (OTESZnPc), are presented and compared with those of unsubstituted zinc phthalocyanine (ZnPc). The presence of triethyleneoxysulphanyl substituents on the ZnPc ring gave rise to higher values of singlet oxygen (˚ ) and photodegradation (˚P d ) quantum yields in DMF. However, TTESZnPc, OTESZnPc and CTESZnPc are less fluorescent than ZnPc, judging from their fluorescence quantum yield (˚F) values. Fluorescence was lower in toluene than in DMF due to aggregation in the former solvent. Triplet quantum yield (˚T) values were found to increase with the presence of substituents on the ZnPc ring, while triplet lifetimes ( T ) were found to vary linearly with the logarithms of solvent viscosities. The fluorescences of the substituted ZnPc complexes were effectively quenched by benzoquinone (BQ), and the quenching data analyzed by the Stern-Volmer equation. The Stern-Volmer constants and the diffusion-controlled bimolecular rate constants were calculated.
Synthetic Metals, 2016
In this study the synthesis and characterization of novel phthalonitrile compound (3) and its metal-free (4), zinc(II) (5), and lead(II) (6) phthalocyanines bearing four 4-(4-methoxyphenylethyl)-5-propyl-2,4dihydro-3H-1,2,4-triazol-3-one groups at peripheral positions were synthesized for the first time. These novel compounds were fully characterized by FT-FT-IR, 1 H NMR, UV-vis and MALDI-TOF mass spectroscopic techniques. Their photochemical and photophysical properties were also investigated in N, N-dimethylformamide solutions. In addition, the effect of 4-(4-methoxyphenylethyl)-5-propyl-2,4dihydro-3H-1,2,4-triazol-3-one groups as substituents and central metal ions (without metal, zinc(II) or lead(II)) in the phthalocyanine cavity on these properties were also compared. The studied zinc(II) or lead (II) phthalocyanines can be potential Type II photosensitizers for photodynamic therapy in cancer applications because these phthalocyanines showed good singlet oxygen generation and appropriate photodegradation. 2016 Elsevier B.V. All rights reserved.
Journal of Photochemistry and Photobiology A: Chemistry, 2012
This work reports on the synthesis and the physicochemical properties of novel unsymmetrically substituted zinc phthalocyanines (complexes 8, 10 and 11) and their symmetrically substituted counterparts (complexes 9, 12 and 13). The new complexes and their counterparts were successfully structurally characterized by IR, NMR, mass spectral and elemental analyses. Low fluorescence quantum yields (0.032) and lifetimes (0.91 ns) were obtained for the symmetrical ZnOTPc (complex 9) compared to the higher fluorescence quantum yields (0.15, 0.13, 0.10, 0.09 and 0.29) and lifetimes (4.4, 1.69, 1.69, 2.16 and 3.23 ns) obtained for ZnMPCPc (8), ZnTDTPc (12), ZnMCapPc (10), ZnMCafPc (11) and ZnTCPPc (13), respectively. All the complexes showed the ability to produce singlet oxygen with the highest triplet quantum yields obtained for 8 and 10 (0.80 and 0.65 respectively). High triplet lifetimes (109-286 s) were obtained for all complexes. Complex 8 showed the longest triplet and fluorescence lifetimes as well the largest triplet state and singlet oxygen quantum yields.