Synthesis and characterization of a new soluble metal-free and metallophthalocyanines bearing biphenyl-4-yl methoxy groups (original) (raw)
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Journal of Organometallic Chemistry, 2011
The synthesis and characterization of new peripherally tetra-4-benzyloxybenzoxy substituted metalfree, zinc and lead phthalocyanines are described for the first time in this study. The influence of various organic solvents and the nature of the central metal ion on the spectroscopic, photophysical and photochemical properties has been investigated. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes of these compounds in different solvents. Photophysical and photochemical properties of phthalocyanine compounds are very useful for photodynamic therapy applications. Especially high singlet oxygen quantum yields are very important for Type II mechanism. The studied phthalocyanine compounds showed good singlet oxygen generation and these compounds show potential as Type II photosensitizers. The fluorescences of the studied compounds are effectively quenched by 1,4-benzoquinone in different solvents.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2012
The synthesis of a new 3,4-(dimethoxyphenylthio) substituted phthalonitrile (1) and its soluble metal free (2), zinc (II) (3), oxo-titanium (IV) (4) and nickel (II) (5) phthalocyanine derivatives are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, 1 H NMR, UV-Vis, fluorescence spectroscopies and mass spectra. General trends are described for fluorescence, photodegradation and singlet oxygen quantum yields and fluorescence lifetimes of oxo-titanium (IV) and zinc (II) phthalocyanine compounds in dimethylsulfoxide (DMSO). The effects of the metal ion on the photophysical and photochemical parameters for these phthalocyanines are also reported.
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.
Dyes and Pigments, 2012
A series of zinc phthalocyanines and corresponding aza-analogues azaphthalocyanines substituted with peripheral 2,6-diisopropylphenoxy substituents containing different functional groups (Br, OCH 3 , and OH) were synthesized and their photophysical properties were investigated. UVevis and 1 H NMR analyses confirmed the non-aggregation behavior of the prepared complexes in most organic solvents. All investigated compounds showed good photophysical and photochemical properties in THF and DMF with F F values in the range of 0.22e0.44 and F D values ranging between 0.42 and 0.57. Hydroxylated compounds showed good solubility in polar solvents including ethanol, methanol, acetone and even in aqueous ethanol mixtures. Absorption spectra in aqueous ethanol indicated presence of only monomers even at very low ethanol content in water (0.5% of ethanol in water). Despite this, no fluorescence occurred from approximately 50% of ethanol in water suggesting presence of aggregates that do not differ from monomers in a shape of absorption spectra.
Dyes and Pigments, 2011
The synthesis, characterization, voltammetric and spectroelectrochemical properties of a novel tetracationic metallophthalocyanine (M ¼ Zn) containing four Schiff's base substituents attached directly on peripheral positions have been presented in this work. The new compounds have been characterized by using elemental analysis, FTIR, 1 H NMR, UVeVis and MALDI-TOF MS spectroscopic data. The electrochemical, in-situ spectroelectrochemical, and in-situ electrocolorimetric measurements on precursors and end products confirm that the complexes exhibit extra electron transfer reaction assignable to the electroactive nitro, amine and Schiff's base groups in addition to the common Pc ring-based processes. Extra conjugation of amine and cinnamaldehyde groups causes both a bathochromic shift (ca. 30 nm) in Q-band maxima and a lower redox potential (ca. À400 mV) in CV measurements.
Synthesis and characterization of new soluble phthalocyanines containing macrocycle units
Polyhedron, 2008
A soluble metal-free phthalocyanine 5 and its metal complexes (Zn, Ni, Co and Cu) 6, 7, 8 and 9 containing eight 16-membered tetrathiamonoaza macrocycles on peripheral substituent positions have been synthesized. The metal-free phthalocyanine 5 was synthesized from 4,5-bis{[2-(1,4,10,13-tetrathia-7-azacyclohexadecan-7-yl)ethyl]oxy}phthalonitrile 4. The metal complexes 6, 7 and 8 were prepared by a tetramerization reaction of the phthalonitrile derivative 4 with appropriate materials. Copper(II) phthalocyanine 9 was prepared by the reaction of 4,5-bis{[2-(1,4,10,13-tetrathia-7-azacyclohexadecan-7yl)ethyl]oxy}-1,2-dibromobenzene 3 with excess CuCN and dry quinoline. Liquid-liquid extraction of several heavy metal ions such as Ag + , Hg 2+ , Pb 2+ , Cd 2+ , Cu 2+ and Zn 2+ with compound 5 was also tested using picrate as the anion of the ion pair. The extraction avidity of 5 for Ag + was found to be highest in the liquid-liquid phase extraction experiments. The new compounds were characterized by a combination of elemental analysis, UV-Vis, FT-IR, NMR and mass spectral data.
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.
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.
Polyhedron, 2013
A dinitrile precursor, 1,2-bis(3-hydroxypropylmercapto)-4,5-dicyanobenzene (3), was synthesized via base-catalyzed nucleophilic aromatic chlorine displacement of 4,5-dichlorophthalonitrile with 3-mercapto-1-propanol. A novel metal-free phthalocyanine (4) (M = 2H) and its metal complexes (5)-(8) (M = Zn, Ni, Cu and Co) were prepared by the cyclotetramerization reaction of (3) with the appropriate materials. The aggregation property of the zinc(II) phthalocyanine (5) was investigated in terms of concentration, Ag + , Hg 2+ , Pb 2+ and Cd 2+ cations and also different solvents, such as dimethylformamide and pyridine. Complexation of the peripheral dithia groups of (5) with Ag + or Pd 2+ yields the pentanuclear complex (9) or (10), respectively. The fluorescence spectrum of compound (5) was also studied. The electrical conductivities of (5)-(10) in air and under vacuum were found to be $10 À9-10 À5 S m À1. All the novel compounds were characterized by elemental analysis, UV-Vis, FT-IR, NMR and MS spectral data and DSC techniques.
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.