Volkan Çakır | Giresun University (original) (raw)
Papers by Volkan Çakır
Peripherally and non-peripherally tetra-substituted zinc(II) phthalocyanines bearing 2-(2-{2-[3-(... more Peripherally and non-peripherally tetra-substituted zinc(II) phthalocyanines bearing 2-(2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy)ethoxy and 2-(2-{2-[3-(diethylamino)phenoxy]ethoxy}ethoxy)ethoxy groups (2a, 5a, 3a and 6a) were synthesized by cyclotetramerization of the corresponding phthalonitriles (2, 5, 3 and 6). Their quaternized ionic derivatives (2b, 5b, 3b and 6b) were also synthesized by the reaction of them with methyl iodide. The novel compounds were characterized by using standard spectroscopic techniques such as FT-IR, 1 H NMR, 13 C NMR, UV-vis, mass and elemental analyses. The obtained quaternized phthalocyanines (2b, 5b, 3b and 6b) showed amphiphilic behaviour with excellent solubility in both organic and aqueous solutions, which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel phthalocyanines were studied in DMSO for both non-ionic and ionic quaternized derivatives. However, these properties were examined in both DMSO and phosphate buffer solution (PBS) for quaternized ionic phthalocyanines. The effects of the positions of substituents ( peripheral or non-peripheral) and the quaternization of the nitrogen atoms on the substituents about their photophysical and photochemical properties were also compared in this study. The bovine serum albumin (BSA) binding behaviours of the studied quaternized ionic zinc(II) phthalocyanines were also described in PBS solutions. The quaternized phthalocyanines (2b, 5b, 3b and 6b) successfully displayed light-dependent photodamage in HeLa and HuH-7 cancer cells in photodynamic therapy treatment. The photosensitivity and the intensity of damage were found directly related to the concentration of the photosensitizers. † Electronic supplementary information (ESI) available. See ; Tel: +90 262 605 3019 9646 | Dalton Trans., 2015, 44, 9646-9658 This journal is
The synthesis and photochemical properties of peripherally and non-peripherally 1,3-bis[3-(dimeth... more 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.
Tetra-substituted zinc (II) phthalocyanines (2a, 3a, 5a and 6a) were synthesized by cyclotetramer... more Tetra-substituted zinc (II) phthalocyanines (2a, 3a, 5a and 6a) were synthesized by cyclotetramerization of phthalonitrile derivatives (2, 3, 5 and 6). These zinc phthalocyanines (2a, 3a, 5a and 6a) were converted into their water-soluble quaternized derivatives (2b, 3b, 5b and 6b) by reaction with methyl iodide. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel compounds were investigated in dimethylsulfoxide for both non-ionic and quaternized ionic complexes and in phosphate buffer saline (PBS) for only quaternized ionic complexes. The effect of the two type substituents with different positions on the photophysical and photochemical properties of these phthalocyanines were compared in this study.
![Research paper thumbnail of Water soluble {2-[3-(diethylamino)phenoxy]ethoxy} substituted zinc(II) phthalocyanine photosensitizers](https://attachments.academia-assets.com/37722272/thumbnails/1.jpg)
](The new peripherally and non-peripherally tetra-{2-[3-(diethylamino)phenoxy] ethoxy} substituted ... more The new peripherally and non-peripherally tetra-{2-[3-(diethylamino)phenoxy] ethoxy} substituted zinc phthalocyanines (2a and 3a) were synthesized by cyclotetramerization of phthalonitrile derivatives (2 and 3). 2-[3-(diethylamino)phenoxy] ethoxy group was chosen as substituent because the quaternization of the diethylamino functionality on the structure of this group produced water soluble zinc phthalocyanines (2b and 3b). The water solubility is very important for many different applications such as photosensitizers in the photodynamic therapy of cancer because the water soluble photosensitizers can be injected directly to the body and they can transport to cancer cells through blood stream. The new compounds were characterized by using elemental analysis, UV-vis, IR, 1 H NMR, 13 C NMR and mass spectroscopies. The photophysical and photochemical properties of these novel photosensitizer compounds were examined in DMSO (both non-ionic and ionic complexes) and in PBS (for ionic complexes) solutions. The investigation of these properties is very important for the usage of the compounds as photosensitizers for PDT because determination of these properties is the first stage of potential of the compounds as photosensitizers. The bovine serum albumin (BSA) and DNA binding behaviour of the studied water soluble zinc (II) phthalocyanines were also investigated in PBS solutions for the determination of biological activity of these compounds.
Metal-free 4 and metallophthalocyanine complexes 5-7 (MPcs, M = Ni, Co, Cu) substituted with the ... more Metal-free 4 and metallophthalocyanine complexes 5-7 (MPcs, M = Ni, Co, Cu) substituted with the electropolymerizable (2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy) group have been synthesized and their structure have been identified by IR, 1 H and 13 C NMR, mass and UV-Vis spectroscopy techniques. The electrochemical characterization of the phthalocyanines sustained the submitted structures of the complexes, since the half wave peak potentials of the redox processes are in harmony with the common electrochemical behavior of MPcs. CoPc gives a metal based reduction process in addition to the ligand based electron transfer processes, which enrich the possible usage of the complex in various electrochemical technologies. All the complexes were coated on the working electrode with an oxidative electopolymerization process during the anodic potential scans.
The synthesis, characterization of newly synthesized metal-free 4 and metallophthalocyanine compl... more The synthesis, characterization of newly synthesized metal-free 4 and metallophthalocyanine complexes 5e7 (MPcs, M ¼ Ni, Co, Cu) have been presented in this work. All the new phthalocyanine compounds are characterized by a combination of IR, 1 H and 13 C NMR, mass and UVeVis spectroscopy techniques. Voltammetric and spectroelectrochemical analyses of phthalocyanines supported the proposed structure of the synthesized complexes. All complexes were oxidatively electropolymerized on the working electrode during the repetitive anodic potential scans. Formation of thin film of the complex as a result of electropolymerization, and controlling the film characters by altering the excitation signals of the voltammetry, changing the working electrode and metal center of the complexes affects the polymerization mechanisms.
The synthesis of a new metal-free, zinc (II), cobalt phthalocyanines and their water soluble quat... more The synthesis of a new metal-free, zinc (II), cobalt phthalocyanines and their water soluble quaternized derivatives 5a, 6a substituted with four crown ether groups are described. The aggregation behavior of these compounds was investigated in different concentrations of DMSO. The effect of solvents on absorption spectra was studied in various organic solvents. Water soluble phthalocyanines 5a and 6a were investigated for their aggregation behavior in DMSO, DMF, water and in various DMSO/water mixtures by comparing their UVeVis spectra. Water soluble phthalocyanines in DMSO and in up to 50 vol.% DMSO/ water are nonaggregated. But increasing amounts of water leads to higher aggregation ratios. Electrochemical properties of phthalocyanines were investigated by cyclic and square wave voltammetry. While cobalt phthalocyanine displayed metal and ring-based redox processes, the other phthalocyanines displayed only ring-based redox processes.
In this study, a new phthalonitrile derivative 3 bearing 1,3-bis[3(dimethylamino)phenoxy]propan-2... more In this study, a new phthalonitrile derivative 3 bearing 1,3-bis[3(dimethylamino)phenoxy]propan-2-ol 1, metal-free phthalocyanine (Pc) 4, metallophthalocyanines (MPcs) 5-7 and their quaternized derivatives 4a-7a were synthesized. Metal-free Pc 4 was prepared by cyclotetramerization of phthalonitrile derivate 3 and MPcs 5-7 were synthesized by heating 3 with NiCl 2 , CoCl 2 and CuCl 2 in npentanol in the presence of 1,8-diazabicyclo[5.4.0]undec-7ene, respectively. Quaternization of the dimethylamino functionality produced quaternized octacationic water soluble metal-free, Ni, Co and Cu Pcs which were soluble in water, DMF, DMSO. The aggregation behaviour of these compounds were investigated in different concentrations of chloroform for metal-free, Ni, Co and Cu Pcs. The effect of solvents on absorption spectra were studied in various organic solvents. The novel compounds were characterized using IR, 1 H-, 13 C NMR, UV-vis and MS spectral data.
The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol subst... more The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituted zinc(II) phthalocyanine complexes (2a and 3a) and their quaternized amphiphilic derivatives (2b and 3b) have been synthesized and characterized using UV-vis, FT-IR, 1 H-NMR, 13 C-NMR, MS spectroscopic data and elemental analysis for the first time. The quaternized complexes (2b and 3b) show excellent solubility in water and DMSO which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines are investigated in dimethylsulfoxide (DMSO) for non-quaternized complexes and in DMSO, phosphate buffered solution (PBS) or PBS þtriton X-100 (TX) solution for quaternized complexes. In this study, the effects of the aggregation of the molecules, quaternization, position of the substituents (peripherally or nonperipherally) and nature of the solvents (DMSO, PBS or PBSþ triton X-100) on the photochemical parameters of the zinc (II) phthalocyanines are also reported. In addition, a spectroscopic investigation of the binding behavior of the quaternized zinc(II) phthalocyanine complexes to bovine serum albumin (BSA) is also presented in this work.
In this study, new iron and cobalt phthalocyanines bearing (2-{2-[3-(dimethylamino)phenoxy]ethoxy... more In this study, new iron and cobalt phthalocyanines bearing (2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy) groups at peripheral positions have been synthesized and characterized by the spectroscopic methods (IR, 1 H NMR, 13 C NMR, UV-vis, mass spectroscopies and elemental analysis). Catalytic activity of Fe(II) and Co(II) phthalocyanines have been investigated in the presence of an oxidant such as TBHP (tert-buthylhydroperoxide), m-CPBA (m-chloroperoxybenzoic acid) and H 2 O 2 (hydrogen peroxide). Fe(II) and Co(II) phthalocyanines exhibit excellent activity and high conversion under mild conditions. Substrate ratio, oxidant ratio, temperature and oxidant type have also been investigated in 3 h and found the best optimum reaction conditions in this catalytic system.
![Research paper thumbnail of New electropolymerizable metal-free and metallophthalocyanines bearing {2-[3-(diethylamino)phenoxy]ethoxy } substituents](https://attachments.academia-assets.com/37722371/thumbnails/1.jpg)
](In this work, metal-free and metallophthalocyanines (Ni, Co, Cu) bearing peripherally tetra subst... more In this work, metal-free and metallophthalocyanines (Ni, Co, Cu) bearing peripherally tetra substituted 4-{2-[3-(diethylamino)phenoxy]ethoxy}groups were synthesized by cyclotetramerization of the corresponding phthalonitrile derivative and their electrochemical, spectroelectrochemical properties were investigated. Phthalocyanines were characterized by a combination of IR, 1 H-NMR, UV-vis and MS spectral data. Diethylamino groups on the substituents of the complexes cause electropolymerization of the complexes on the working electrode during the oxidation reactions. Changing the potential window of the voltammetric cycles alters the electropolymerization mechanisms. Types of the metal center of the complexes also affect the electropolymerization mechanism. Spectroelectrochemical measurements were performed to assign the redox processes and spectroscopic responses of the electropolymerization processes.
The novel phthalonitrile derivatives (2 and 3) bearing 2-[3-(dimethylamino)phenoxy]ethanol substi... more The novel phthalonitrile derivatives (2 and 3) bearing 2-[3-(dimethylamino)phenoxy]ethanol substituents on the 3 and 4 positions have been synthesized. The novel peripherally and non-peripherally tetra-{2-[3-(dimethylamino)phenoxy]} substituted zinc phthalocyanines (2a and 3a) were also synthesized by cyclotetramerization of phthalonitrile derivatives (2 and 3). The obtained new zinc phthalocyanines (2a and 3a) were converted into water-soluble quaternized products (2b and 3b). The new compounds have been characterized by combination of spectroscopic data including UVeVis, IR, 1 H NMR, 13 C NMR, MS spectroscopic data and elemental analysis as well. The photophysical and photochemical properties of newly synthesized zinc phthalocyanines were investigated in DMSO for non-ionic and in both DMSO and phosphate buffer solution (PBS) for ionic compounds. The obtained ionic complexes (2b, 3b) show excellent solubility in both organic and aqueous solutions which is very useful for the treatment of cancer by photodynamic therapy (PDT).
The synthesis and characterization of novel peripherally-tetra substituted metal-free 4 and metal... more The synthesis and characterization of novel peripherally-tetra substituted metal-free 4 and metallophthalocyanines 5e7 are described for the first time in this study. All the new compounds are characterized by a combination of IR, 1 H and 13 C NMR, mass and UVevis spectroscopy techniques. Electrochemical and spectroelectrochemical properties of metal-free, nickel(II), cobalt(II) and copper(II) phthalocyanines were investigated by using cyclic voltammetry and square wave voltammetry techniques. While all complexes give common reduction processes, they electropolymerized on the working electrode. Applied potentials and type of the metal center of the complexes affect the electropolymerization mechanism. Spectroelectrochemical and electrocolorimetric measurements exhibit that electrogenerated anionic species of the complexes have distinct color differences which are desire factors for electrochromic application of the complexes.
In this study, new 1,3-bis[3-(diethylamino)phenoxy]propan-2-ol 1 and phthalonitrile derivative 3 ... more In this study, new 1,3-bis[3-(diethylamino)phenoxy]propan-2-ol 1 and phthalonitrile derivative 3 bearing 1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituent at peripheral position have been synthesized. The synthesis, characterization of the tetra-4-(2-[3-(diethylamino)phenoxy]-1-{[3-(diethylamino)phenoxy]methyl}ethoxy) substituted metal-free 4 and metallophthalocyanines 5, 6, 7, (MPcs, M = Ni, Co, Cu) are reported for the first time. These new metal-free and metallophthalocyanines 4-7 were converted into water soluble quaternized products by the reaction with methyl iodide 4a-7a. The metal-free phthalocyanine 4 was prepared from phthalonitrile derivative 3 in n-pentanol with a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7ene (DBU). Metallophthalocyanines 5-7 were prepared by cyclotetramerization of 3 with the corresponding metal salts (NiCl 2 , CoCl 2 , CuCl 2 ) in n-pentanol with a catalytic amount of DBU. The aggregation behaviours of the phthalocyanine complexes were studied in different solvents and concentrations. The new compounds have been characterized by using UV-vis, IR, 1 H NMR, 13 C NMR, MS spectroscopic data and elemental analysis.
The synthesis of new metal-free, nickel, zinc, cobalt and copper phthalocyanines with four 6oxyqu... more The synthesis of new metal-free, nickel, zinc, cobalt and copper phthalocyanines with four 6oxyquinoline groups on the non-peripheral position were prepared by cyclotetramerization of a novel 3-(quinolin-6-yloxy)phthalonitrile. All new compounds were characterized by the ways of IR, 1 H NMR, 13 C NMR and MS spectral data, all of which were compatible with the proposed structures. Electrochemical properties of metal-free, Ni(II) and Zn(II) phthalocyanines were investigated by using cyclic voltammetry and differential pulse voltammetry techniques. The metal-free phthalocyanine exhibits two reversible Pc ring-based one-electron reduction couples. The Ni(II) and Zn(II) phthalocyanines give very similar voltammetric responses with slightly potential shift due to the different metal center.
This work reports on a new symmetrically substituted metal-free phthalocyanine and its transition... more This work reports on a new symmetrically substituted metal-free phthalocyanine and its transition metal complexes which were prepared by a condensation of N,N 0 -[propan-1,3-diilbis(tiyoetan-2,1-diil)]bis(4methylbenzenesulfonamid) (1) and 1,2-bis (2-iodomercaptoethyl)-4,5-dicyanobenzene (2) with NiCl 2 , ZnCl 2 , CoCl 2 , CuCl 2 ,and PbO salts in 2-(dimethylamino)ethanol, respectively. The phthalocyanines bearing thia and aza donor atoms at the peripheral position were characterized by IR, UVeVis, 1 H NMR, 13 C NMR, Mass spectra, and elemental analysis data. The thermal behaviors of 4e9 were investigated by TG/DTA. Novel phthalocyanines were also investigated for enlightening their possible biological activities by employing antimicrobial (antibacterial and antifungal), antineoplastic and antioxidative assays. Of all tested, four samples exhibited antimicrobial activity against test microorganisms, among which, Branhamella catarrhalis was the most sensitive one with a MIC value around 0.312 mg/mL followed by a yeast, Candida albicans (MIC. 0.625 mg/mL). Due to their colored nature, the samples were found not to be applicable for antioxidative and antineoplastic assays.
The synthesis and characterization of peripherally tetra-biphenyl-4-yl-methoxy substituted metal-... more The synthesis and characterization of peripherally tetra-biphenyl-4-yl-methoxy substituted metal-free (4), Ni(II) (5), Cu(II) (6), Zn(II) (7), Co(II) (8) and Pb(II) (9) phthalocyanine derivatives are reported. These new phthalocyanine derivatives show the enhanced solubility in organic solvents and they have been characterized by a combination of IR, 1 H NMR, 13 C NMR, UVevis, mass spectral data, elemental analysis and thermal analysis methods (TG/DTA). The photophysical (fluorescence quantum yield and lifetime) and photochemical (singlet oxygen generation and photodegradation quantum yield) properties of tetra-biphenyl-4-yl-methoxy substituted zinc (II) phthalocyanine derivative are also investigated. The fluorescence of this phthalocyanine derivative is effectively quenched by addition of 1,4-benzoquinone (BQ).
Peripherally and non-peripherally tetra-substituted zinc(II) phthalocyanines bearing 2-(2-{2-[3-(... more Peripherally and non-peripherally tetra-substituted zinc(II) phthalocyanines bearing 2-(2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy)ethoxy and 2-(2-{2-[3-(diethylamino)phenoxy]ethoxy}ethoxy)ethoxy groups (2a, 5a, 3a and 6a) were synthesized by cyclotetramerization of the corresponding phthalonitriles (2, 5, 3 and 6). Their quaternized ionic derivatives (2b, 5b, 3b and 6b) were also synthesized by the reaction of them with methyl iodide. The novel compounds were characterized by using standard spectroscopic techniques such as FT-IR, 1 H NMR, 13 C NMR, UV-vis, mass and elemental analyses. The obtained quaternized phthalocyanines (2b, 5b, 3b and 6b) showed amphiphilic behaviour with excellent solubility in both organic and aqueous solutions, which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel phthalocyanines were studied in DMSO for both non-ionic and ionic quaternized derivatives. However, these properties were examined in both DMSO and phosphate buffer solution (PBS) for quaternized ionic phthalocyanines. The effects of the positions of substituents ( peripheral or non-peripheral) and the quaternization of the nitrogen atoms on the substituents about their photophysical and photochemical properties were also compared in this study. The bovine serum albumin (BSA) binding behaviours of the studied quaternized ionic zinc(II) phthalocyanines were also described in PBS solutions. The quaternized phthalocyanines (2b, 5b, 3b and 6b) successfully displayed light-dependent photodamage in HeLa and HuH-7 cancer cells in photodynamic therapy treatment. The photosensitivity and the intensity of damage were found directly related to the concentration of the photosensitizers. † Electronic supplementary information (ESI) available. See ; Tel: +90 262 605 3019 9646 | Dalton Trans., 2015, 44, 9646-9658 This journal is
The synthesis and photochemical properties of peripherally and non-peripherally 1,3-bis[3-(dimeth... more 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.
Tetra-substituted zinc (II) phthalocyanines (2a, 3a, 5a and 6a) were synthesized by cyclotetramer... more Tetra-substituted zinc (II) phthalocyanines (2a, 3a, 5a and 6a) were synthesized by cyclotetramerization of phthalonitrile derivatives (2, 3, 5 and 6). These zinc phthalocyanines (2a, 3a, 5a and 6a) were converted into their water-soluble quaternized derivatives (2b, 3b, 5b and 6b) by reaction with methyl iodide. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel compounds were investigated in dimethylsulfoxide for both non-ionic and quaternized ionic complexes and in phosphate buffer saline (PBS) for only quaternized ionic complexes. The effect of the two type substituents with different positions on the photophysical and photochemical properties of these phthalocyanines were compared in this study.
The new peripherally and non-peripherally tetra-{2-[3-(diethylamino)phenoxy] ethoxy} substituted ... more The new peripherally and non-peripherally tetra-{2-[3-(diethylamino)phenoxy] ethoxy} substituted zinc phthalocyanines (2a and 3a) were synthesized by cyclotetramerization of phthalonitrile derivatives (2 and 3). 2-[3-(diethylamino)phenoxy] ethoxy group was chosen as substituent because the quaternization of the diethylamino functionality on the structure of this group produced water soluble zinc phthalocyanines (2b and 3b). The water solubility is very important for many different applications such as photosensitizers in the photodynamic therapy of cancer because the water soluble photosensitizers can be injected directly to the body and they can transport to cancer cells through blood stream. The new compounds were characterized by using elemental analysis, UV-vis, IR, 1 H NMR, 13 C NMR and mass spectroscopies. The photophysical and photochemical properties of these novel photosensitizer compounds were examined in DMSO (both non-ionic and ionic complexes) and in PBS (for ionic complexes) solutions. The investigation of these properties is very important for the usage of the compounds as photosensitizers for PDT because determination of these properties is the first stage of potential of the compounds as photosensitizers. The bovine serum albumin (BSA) and DNA binding behaviour of the studied water soluble zinc (II) phthalocyanines were also investigated in PBS solutions for the determination of biological activity of these compounds.
Metal-free 4 and metallophthalocyanine complexes 5-7 (MPcs, M = Ni, Co, Cu) substituted with the ... more Metal-free 4 and metallophthalocyanine complexes 5-7 (MPcs, M = Ni, Co, Cu) substituted with the electropolymerizable (2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy) group have been synthesized and their structure have been identified by IR, 1 H and 13 C NMR, mass and UV-Vis spectroscopy techniques. The electrochemical characterization of the phthalocyanines sustained the submitted structures of the complexes, since the half wave peak potentials of the redox processes are in harmony with the common electrochemical behavior of MPcs. CoPc gives a metal based reduction process in addition to the ligand based electron transfer processes, which enrich the possible usage of the complex in various electrochemical technologies. All the complexes were coated on the working electrode with an oxidative electopolymerization process during the anodic potential scans.
The synthesis, characterization of newly synthesized metal-free 4 and metallophthalocyanine compl... more The synthesis, characterization of newly synthesized metal-free 4 and metallophthalocyanine complexes 5e7 (MPcs, M ¼ Ni, Co, Cu) have been presented in this work. All the new phthalocyanine compounds are characterized by a combination of IR, 1 H and 13 C NMR, mass and UVeVis spectroscopy techniques. Voltammetric and spectroelectrochemical analyses of phthalocyanines supported the proposed structure of the synthesized complexes. All complexes were oxidatively electropolymerized on the working electrode during the repetitive anodic potential scans. Formation of thin film of the complex as a result of electropolymerization, and controlling the film characters by altering the excitation signals of the voltammetry, changing the working electrode and metal center of the complexes affects the polymerization mechanisms.
The synthesis of a new metal-free, zinc (II), cobalt phthalocyanines and their water soluble quat... more The synthesis of a new metal-free, zinc (II), cobalt phthalocyanines and their water soluble quaternized derivatives 5a, 6a substituted with four crown ether groups are described. The aggregation behavior of these compounds was investigated in different concentrations of DMSO. The effect of solvents on absorption spectra was studied in various organic solvents. Water soluble phthalocyanines 5a and 6a were investigated for their aggregation behavior in DMSO, DMF, water and in various DMSO/water mixtures by comparing their UVeVis spectra. Water soluble phthalocyanines in DMSO and in up to 50 vol.% DMSO/ water are nonaggregated. But increasing amounts of water leads to higher aggregation ratios. Electrochemical properties of phthalocyanines were investigated by cyclic and square wave voltammetry. While cobalt phthalocyanine displayed metal and ring-based redox processes, the other phthalocyanines displayed only ring-based redox processes.
In this study, a new phthalonitrile derivative 3 bearing 1,3-bis[3(dimethylamino)phenoxy]propan-2... more In this study, a new phthalonitrile derivative 3 bearing 1,3-bis[3(dimethylamino)phenoxy]propan-2-ol 1, metal-free phthalocyanine (Pc) 4, metallophthalocyanines (MPcs) 5-7 and their quaternized derivatives 4a-7a were synthesized. Metal-free Pc 4 was prepared by cyclotetramerization of phthalonitrile derivate 3 and MPcs 5-7 were synthesized by heating 3 with NiCl 2 , CoCl 2 and CuCl 2 in npentanol in the presence of 1,8-diazabicyclo[5.4.0]undec-7ene, respectively. Quaternization of the dimethylamino functionality produced quaternized octacationic water soluble metal-free, Ni, Co and Cu Pcs which were soluble in water, DMF, DMSO. The aggregation behaviour of these compounds were investigated in different concentrations of chloroform for metal-free, Ni, Co and Cu Pcs. The effect of solvents on absorption spectra were studied in various organic solvents. The novel compounds were characterized using IR, 1 H-, 13 C NMR, UV-vis and MS spectral data.
The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol subst... more The new peripherally and non-peripherally tetra-1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituted zinc(II) phthalocyanine complexes (2a and 3a) and their quaternized amphiphilic derivatives (2b and 3b) have been synthesized and characterized using UV-vis, FT-IR, 1 H-NMR, 13 C-NMR, MS spectroscopic data and elemental analysis for the first time. The quaternized complexes (2b and 3b) show excellent solubility in water and DMSO which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines are investigated in dimethylsulfoxide (DMSO) for non-quaternized complexes and in DMSO, phosphate buffered solution (PBS) or PBS þtriton X-100 (TX) solution for quaternized complexes. In this study, the effects of the aggregation of the molecules, quaternization, position of the substituents (peripherally or nonperipherally) and nature of the solvents (DMSO, PBS or PBSþ triton X-100) on the photochemical parameters of the zinc (II) phthalocyanines are also reported. In addition, a spectroscopic investigation of the binding behavior of the quaternized zinc(II) phthalocyanine complexes to bovine serum albumin (BSA) is also presented in this work.
In this study, new iron and cobalt phthalocyanines bearing (2-{2-[3-(dimethylamino)phenoxy]ethoxy... more In this study, new iron and cobalt phthalocyanines bearing (2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy) groups at peripheral positions have been synthesized and characterized by the spectroscopic methods (IR, 1 H NMR, 13 C NMR, UV-vis, mass spectroscopies and elemental analysis). Catalytic activity of Fe(II) and Co(II) phthalocyanines have been investigated in the presence of an oxidant such as TBHP (tert-buthylhydroperoxide), m-CPBA (m-chloroperoxybenzoic acid) and H 2 O 2 (hydrogen peroxide). Fe(II) and Co(II) phthalocyanines exhibit excellent activity and high conversion under mild conditions. Substrate ratio, oxidant ratio, temperature and oxidant type have also been investigated in 3 h and found the best optimum reaction conditions in this catalytic system.
In this work, metal-free and metallophthalocyanines (Ni, Co, Cu) bearing peripherally tetra subst... more In this work, metal-free and metallophthalocyanines (Ni, Co, Cu) bearing peripherally tetra substituted 4-{2-[3-(diethylamino)phenoxy]ethoxy}groups were synthesized by cyclotetramerization of the corresponding phthalonitrile derivative and their electrochemical, spectroelectrochemical properties were investigated. Phthalocyanines were characterized by a combination of IR, 1 H-NMR, UV-vis and MS spectral data. Diethylamino groups on the substituents of the complexes cause electropolymerization of the complexes on the working electrode during the oxidation reactions. Changing the potential window of the voltammetric cycles alters the electropolymerization mechanisms. Types of the metal center of the complexes also affect the electropolymerization mechanism. Spectroelectrochemical measurements were performed to assign the redox processes and spectroscopic responses of the electropolymerization processes.
The novel phthalonitrile derivatives (2 and 3) bearing 2-[3-(dimethylamino)phenoxy]ethanol substi... more The novel phthalonitrile derivatives (2 and 3) bearing 2-[3-(dimethylamino)phenoxy]ethanol substituents on the 3 and 4 positions have been synthesized. The novel peripherally and non-peripherally tetra-{2-[3-(dimethylamino)phenoxy]} substituted zinc phthalocyanines (2a and 3a) were also synthesized by cyclotetramerization of phthalonitrile derivatives (2 and 3). The obtained new zinc phthalocyanines (2a and 3a) were converted into water-soluble quaternized products (2b and 3b). The new compounds have been characterized by combination of spectroscopic data including UVeVis, IR, 1 H NMR, 13 C NMR, MS spectroscopic data and elemental analysis as well. The photophysical and photochemical properties of newly synthesized zinc phthalocyanines were investigated in DMSO for non-ionic and in both DMSO and phosphate buffer solution (PBS) for ionic compounds. The obtained ionic complexes (2b, 3b) show excellent solubility in both organic and aqueous solutions which is very useful for the treatment of cancer by photodynamic therapy (PDT).
The synthesis and characterization of novel peripherally-tetra substituted metal-free 4 and metal... more The synthesis and characterization of novel peripherally-tetra substituted metal-free 4 and metallophthalocyanines 5e7 are described for the first time in this study. All the new compounds are characterized by a combination of IR, 1 H and 13 C NMR, mass and UVevis spectroscopy techniques. Electrochemical and spectroelectrochemical properties of metal-free, nickel(II), cobalt(II) and copper(II) phthalocyanines were investigated by using cyclic voltammetry and square wave voltammetry techniques. While all complexes give common reduction processes, they electropolymerized on the working electrode. Applied potentials and type of the metal center of the complexes affect the electropolymerization mechanism. Spectroelectrochemical and electrocolorimetric measurements exhibit that electrogenerated anionic species of the complexes have distinct color differences which are desire factors for electrochromic application of the complexes.
In this study, new 1,3-bis[3-(diethylamino)phenoxy]propan-2-ol 1 and phthalonitrile derivative 3 ... more In this study, new 1,3-bis[3-(diethylamino)phenoxy]propan-2-ol 1 and phthalonitrile derivative 3 bearing 1,3-bis[3-(diethylamino)phenoxy]propan-2-ol substituent at peripheral position have been synthesized. The synthesis, characterization of the tetra-4-(2-[3-(diethylamino)phenoxy]-1-{[3-(diethylamino)phenoxy]methyl}ethoxy) substituted metal-free 4 and metallophthalocyanines 5, 6, 7, (MPcs, M = Ni, Co, Cu) are reported for the first time. These new metal-free and metallophthalocyanines 4-7 were converted into water soluble quaternized products by the reaction with methyl iodide 4a-7a. The metal-free phthalocyanine 4 was prepared from phthalonitrile derivative 3 in n-pentanol with a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7ene (DBU). Metallophthalocyanines 5-7 were prepared by cyclotetramerization of 3 with the corresponding metal salts (NiCl 2 , CoCl 2 , CuCl 2 ) in n-pentanol with a catalytic amount of DBU. The aggregation behaviours of the phthalocyanine complexes were studied in different solvents and concentrations. The new compounds have been characterized by using UV-vis, IR, 1 H NMR, 13 C NMR, MS spectroscopic data and elemental analysis.
The synthesis of new metal-free, nickel, zinc, cobalt and copper phthalocyanines with four 6oxyqu... more The synthesis of new metal-free, nickel, zinc, cobalt and copper phthalocyanines with four 6oxyquinoline groups on the non-peripheral position were prepared by cyclotetramerization of a novel 3-(quinolin-6-yloxy)phthalonitrile. All new compounds were characterized by the ways of IR, 1 H NMR, 13 C NMR and MS spectral data, all of which were compatible with the proposed structures. Electrochemical properties of metal-free, Ni(II) and Zn(II) phthalocyanines were investigated by using cyclic voltammetry and differential pulse voltammetry techniques. The metal-free phthalocyanine exhibits two reversible Pc ring-based one-electron reduction couples. The Ni(II) and Zn(II) phthalocyanines give very similar voltammetric responses with slightly potential shift due to the different metal center.
This work reports on a new symmetrically substituted metal-free phthalocyanine and its transition... more This work reports on a new symmetrically substituted metal-free phthalocyanine and its transition metal complexes which were prepared by a condensation of N,N 0 -[propan-1,3-diilbis(tiyoetan-2,1-diil)]bis(4methylbenzenesulfonamid) (1) and 1,2-bis (2-iodomercaptoethyl)-4,5-dicyanobenzene (2) with NiCl 2 , ZnCl 2 , CoCl 2 , CuCl 2 ,and PbO salts in 2-(dimethylamino)ethanol, respectively. The phthalocyanines bearing thia and aza donor atoms at the peripheral position were characterized by IR, UVeVis, 1 H NMR, 13 C NMR, Mass spectra, and elemental analysis data. The thermal behaviors of 4e9 were investigated by TG/DTA. Novel phthalocyanines were also investigated for enlightening their possible biological activities by employing antimicrobial (antibacterial and antifungal), antineoplastic and antioxidative assays. Of all tested, four samples exhibited antimicrobial activity against test microorganisms, among which, Branhamella catarrhalis was the most sensitive one with a MIC value around 0.312 mg/mL followed by a yeast, Candida albicans (MIC. 0.625 mg/mL). Due to their colored nature, the samples were found not to be applicable for antioxidative and antineoplastic assays.
The synthesis and characterization of peripherally tetra-biphenyl-4-yl-methoxy substituted metal-... more The synthesis and characterization of peripherally tetra-biphenyl-4-yl-methoxy substituted metal-free (4), Ni(II) (5), Cu(II) (6), Zn(II) (7), Co(II) (8) and Pb(II) (9) phthalocyanine derivatives are reported. These new phthalocyanine derivatives show the enhanced solubility in organic solvents and they have been characterized by a combination of IR, 1 H NMR, 13 C NMR, UVevis, mass spectral data, elemental analysis and thermal analysis methods (TG/DTA). The photophysical (fluorescence quantum yield and lifetime) and photochemical (singlet oxygen generation and photodegradation quantum yield) properties of tetra-biphenyl-4-yl-methoxy substituted zinc (II) phthalocyanine derivative are also investigated. The fluorescence of this phthalocyanine derivative is effectively quenched by addition of 1,4-benzoquinone (BQ).