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Novel 4-(5-(pyridin-3-yl)-4-p-tolyl-4H-1,2,4-triazol-3-ylthio) substituted phthalonitrile (3) and it’s zinc(II) (4) and copper(II) (5) metallo-phthalocyanine derivatives were synthesized. Spectroscopic and electrochemical characterizations were performed to support the proposed structures of the complexes. Electrochemical properties of metallo-phthalocyanines were determined with cyclic and square wave voltammetry techniques and the effect of metal centers on results were investigated. It was observed that both complexes illustrated Pc based redox processes due to the redox inactivity of the metal centers. Redox assignments were supported with in-situ spectroelectrochemical measurements. Electrochemical and spectroelectrochemical responses of the complexes showed that while both complexes were aggregated in dimethyl formamide, aggregation tendency of CuPc was more than ZnPc. The in-situ spectroelectrochemical results showed that these complexes have potential to be used as electrochromic material in smart glass technologies.

Phthalonitrile (3) including 4-(4-fluorophenyl)-5-(4-methoxyphenyl)-4H-1,2,4-triazole-3-thio substituent and its peripherally tetra substituted metal-free (4), zinc(II) (5) and lead(II) (6) phthalocyanine derivatives were prepared and characterized by FTIR, mass, 1H-NMR and 13C-NMR spectroscopic data. All studied phthalocyanines had good solubility in common organic solvents and did not aggregate. The photophysical and photochemical behaviors of the phthalocyanine complexes (4–6) were examined in DMSO to determinate their PDT potential. Singlet oxygen, fluorescence and photodegradation quantum yields showed that zinc(II) phthalocyanine (5) has potential as Type II photosensitizer for PDT applications.

The presence of nitro compounds and such commercial dyes as Congo red, methylene blue, methyl orange and methyl red in water/wastewater causes environmental issues. The treatment of such industrial contaminants, new efficient hybrid catalysts are designed by Research groups all around the world. For this aim, a large of catalyst systems were designed and their water treatment capacities were investigated. As a part of Green Chemistry approach, food wastes could be used for production of porous carbon materials. In this work, a palladium/activated carbon hybrid catalyst (AC–Pd) was prepared and characterized by XRD, SEM/EDS and TEM. It was found from TEM analysis that the average particle size of AC–Pd hybrid was about 54 nm. The reduction capacity of AC–Pd for nitroarenes and organic dyes was investigated by UV–Vis. spectroscopy in aqueous media. According to catalytic tests results, AC–Pd nanocatalyst could be used in reduction of both nitro compounds and organic dyes.

The 1,4-benzodioxane substituted phthalonitrile compound (3) and non-peripherally tetra substituted cobalt(II) (4), nickel(II) (5) and copper(II) (6) phthalocyanine complexes were synthesized. The structural characterization of the compounds was performed by using various spectroscopic techniques. The electron transfer properties of the phthalocyanine complexes (4–6) were investigated by voltammetric and in situ spectroelectrochemical measurements. The electrochemical and spectroelectrochemical properties of the non-peripherally tetra substituted metallo-phthalocyanines (4–6) having redox active and inactive metal center were compared with each other in terms of electrochemical responses and the differences were revealed.

Cellulose acetate aerogel (CAA) regenerated with toluene solvent was first obtained and analysed in this work using several measurement techniques. CAA, a “green” and environmentally friendly material, with high thermal stability, water absorbency and a porous structure is a hopeful candidate as a superabsorbent and potential heat insulator for various applications. The obtained porous aerogel with a notable surface area (312.5 m2/g) is thermally stable up to about 300 °C and super-absorbent (72.0 g water/1.0 g sample). Thereby, the present study can play an important role in developing production of cellulose acetate based “green” absorbent and potential aerogel materials for heat insulating. Moreover, this process is handily available at low cost, sustainable and favourable for many applications.

In this study, novel triazole peripherally substituted phthalocyanine zinc(II) complexes 3(a-d) were synthesized from four different phthalonitrile derivative and characterized by FT-IR NMR, MALDI-TOF, UV–Vis methods. Aggregation-concentration relations of the compounds 3(a-d) were investigated by UV–Vis spectroscopy. Fluorescence quenching properties of the phthalocyanines 3(a-d) were studied and fluorescence quantum yields were calculated by comparative method. Photodegradation quantum yields of the compound 3(a-d) were calculated. In addition, singlet oxygen quantum yields of the compounds 3(a-d) were measured by comparative method by using 1,3-diphenylisobenzofuran (DPBF) as singlet oxygen quencher. In this work, it has been observed that the synthesized novel phthalocyanines have higher quantum yield values (the range of 0.8–0.85) compared to the Zn (II) complex of unsubstituted phthalocyanine (0.67). Especially the compound 3d substituted tolyl group has the highest singlet oxygen quantum yield (0.85) seen rarely in literature.

In this study, the synthesis and characterization of novel [1,2,3] triazole substituted phthalonitrile compound (3) and non-peripherally tetra 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxyphenethyl methacrylate substituted lead(II) (4), nickel(II) (5) and copper(II) (6) phthalocyanine derivatives were achieved. The new compounds were characterized by using FT-IR, 1H-NMR, 13C-NMR, UV–Vis and mass spectra. The electrochemical properties of novel non-peripherally tetra [1,2,3] triazole substituted metallo phthalocyanines (4–6) was determined by cyclic voltammetry (CV) and square-wave voltammetry (SWV) for the first time in this study. The results show that all the complexes (4–6) have ligand-based diffusion controlled electron transfer properties. The color changes related to the redox processes were also recorded with in-situ electrocolorimetric measurements. When the spectral changes are compared with each other, it is clear that all complexes show Pc based electron transfer reactions. There are slight differences between the spectra of the complexes due to the different nature of the metal centers of the complexes. The electrochemical and in-situ UV–Vis spectral change of complexes (4–6) indicated that they have applicability in electrochemical technologies.

A Pd/Cr2O3 hybrid catalyst for cyanation reaction of some aryl halides was synthesized and characterized by XRD, SEM/EDS and TEM. The porous structure of the catalyst was also investigated by BET analysis. All XRD characteristic lines were obtained for Cr2O3 and Pd/Cr2O3 hybrid in good agreement with the reference XRD data. It was found that average particle size of Pd/Cr2O3 composite was about 22 nm. The catalytic efficiency of the Pd/Cr2O3–catalyzed cyanation reaction was evaluated for some m- and p-substituted aryl halides. The influence of solvent, reaction time, and base on the activity of the Pd/Cr2O3 catalyst was investigated, and the optimal reaction conditions were systematically obtained. Catalytic investigations showed that Pd/Cr2O3 hybrid can exhibit very good catalytic performance for cyanation reaction of aryl halides with a high yield of around 90%, and retained its catalytic activity throughout successive 5 cycles. Comparative TEM images of Pd/Cr2O3 hybrid catalyst, as-synthesized and after 5th cycle, showed that nano-sized structure of Pd/Cr2O3 catalyst was protected without significant change.

AKCAY, Hakki Turker/0000-0002-8502-9608 WOS: 000443574000012 In this study, the novel peripherally 4-[(2-methyl-1H-benzimidazol-1-yl)methoxy] substituted Zn(II) (3) Cu(II) (4), Co(II) (5) phthalocyanines were prepared and their structures were characterized spectro-scopically. The light absorption behaviors of the synthesized compounds (3-6) were studied by UV-Vis spectroscopy in the different concentration and different solvents were studied also. In addition, the urease inhibition activities of the synthesized compounds were also investigated. Among the synthesized molecules, compound 5 showed the best inhibitory effect against jack bean urease with IC50 values of 0.0034 +/- 0.0010 mu M. (C) 2018 Elsevier B.V. All rights reserved. Recep Tayyip Erdogan Universitesi - Research Funding [FBA-2017-788] This study was supported by Recep Tayyip Erdogan Universitesi - Research Funding - (Project no FBA-2017-788).

In the present study novel tetra 4-(4-fluorophenyl)-5-(4-methoxyphenyl)-4H-1,2,4-triazole-3-thio substituted non-peripherally metal free (4), zinc(II) (5), lead (II) (6) and copper(II) (7) phthalocyanines were synthesized. The obtained novel compounds were characterized by a combination of FT-IR, 1H NMR, UV–Vis and MALDI-TOF techniques. The redox properties of the complexes have been investigated via cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemistry. The compounds displayed ring-based, reversible and/or quasi-reversible reduction and oxidation processes and aggregation of the complexes influenced the redox character of the processes. The color changes during the redox processes of metallo phthalocyanine were recorded by in-situ spectroelectrochemical measurements. In situ UV–vis spectroelectrochemical measurements, which was associated with color change of the complexes, showed their applicability in the fields of the electrochemical technologies.

In this study, the novel peripherally tetra 4-isopropylbenzyloxy substituted metal-free (4) zinc(II) (5) and oxo-titanium(IV) (6) phthalocyanine complexes were synthesized. Furthermore, the axially 4-isopropylbenzyloxy substituted silicon(IV) phthalocyanine derivative (7) was also synthesized. These novel compounds were characterized by different spectroscopic methods such as FT-IR, 1H NMR, UV–vis and mass. The spectroscopic, photophysical and photochemical properties including electronic absorption, steady state fluorescence, singlet oxygen generation and photostability were studied in toluene.

In this study novel substituted phthalonitrile (3) and non-peripherally tetra 5-Methyl-1,3,4-thiadiazole substituted copper(II) (4), iron(II) (5) and oxo-titanium (IV) (6) phthalocyanines were synthesized. These novel compounds were fully characterized by FT-IR, 1H NMR, UV–vis and MALDI-TOF mass spectroscopic techniques. Voltammetric and in situ spectroelectrochemical measurements were performed for metallo-phthalocyanines (4–6). TiIVOPc and FeIIPc showed metal-based and ligand-based electron transfer reactions while CuIIPc shows only ligand-based electron transfer reaction. Voltammetric measurements indicated that the complexes have reversible, diffusion controlled and one-electron redox reactions. The assignments of the redox processes and color of the electrogenerated species of the complexes were determined with in-situ spectroelectrochemical and electrocolorimetric measurements. These measurements showed that the complexes can be used as the electrochromic materials for various display technologies.

In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine ( 4) and its zinc(II) ( 5) , copper(II) ( 6) and cobalt(II) ( 7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1 H-NMR, UV–vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. Co II Pc went [Co II Pc −2 ]/[Co I Pc −2 ] 1- , [Co I Pc −2 ] 1- /[Co I Pc −3 ] 2- , [Co I Pc −3 ] 2- /[Co I Pc −4 ] 3- and [Co II Pc −2 ]/[Co II Pc −2 ] 1+ reduction and oxidation processes respectively. Differently Zn II Pc only showed four ligand-based reductions and two ligand based oxidation processes.

AKCAY, Hakki Turker/0000-0002-8502-9608; Hokelek, Tuncer/0000-0002-8602-4382; Vazquez-Lopez, Ezequiel M./0000-0002-6012-0931 WOS: 000385901800063 Heterocyclic phthalonitrile derivatives are important precursors in synthesis of new photoactive phthalocyanine compounds. In this study, novel phthalonitrile compound bearing triazole moiety was synthesized and characterized by using spectroscopic techniques such as FT-IR and NMR. The molecular structures of the title compound was analyzed crystallographically and compared with the structural parameters obtained computationally. The orbital energies, electronic absorptions, atomic charge parameters, vibrational frequencies, ground state transitions, H-1 and C-13 NMR chemical shifts and NBO analysis were computed by using DFT (Density Functional Theory) calculation and compared with the experimental results. (C) 2016 Elsevier B.V. All rights reserved. Recep Tayyip Erdogan UniversityRecep Tayyip Erdogan University [2014.101.16.01] This study was supported by Recep Tayyip Erdogan University - Research Funding - (Project no 2014.101.16.01).

In this study, novel peripherally tetra-(5-chloro-2-(2,4-dichlorophenoxy)phenol) substituted metal-free (4) , zinc(II) (5) and lead(II) (6) phthalocyanine derivatives were synthesised. The novel phthalocyanines (4–6) were characterised by general spectroscopic methods such as IR, 1 H NMR, UV–vis, mass spectrometry and elemental analysis. Once the solubilities of the compounds were investigated, it was noticed that they have excellent solubility and did not tend to aggregation behaviour in common solvents. The photophysical and photochemical properties of novel phthalocyanines (4–6) were investigated in dimethysulfoxide. The effects of substituted 5-chloro-2-(2,4-dichlorophenoxy)phenoxy group and central metal ion [zinc(II)/lead(II)] on photophysical and photochemical properties of the novel phthalocyanines have also been examined, and the results were compared with unsubstituted zinc(II) phthalocyanine. According to photophysical and photochemical investigation results, it was observed that the novel phthalocyanines (4–6) have a potential for PDT application.

AKCAY, Hakki Turker/0000-0002-8502-9608 WOS: 000513010500102 PubMed: 31806475 In this study, novel peripherally 4-[(1H-benzimidazol-1-yl)methoxy] substituted Zn(II) (3) Cu(II) (4) and Co(II) (5) phthalocyanines were prepared and their structures were characterized spectroscopically. The light absorption behaviors of the synthesized compounds (3-5) were studied by UV-Vis spectroscopy at different concentrations in different solvents. The urease inhibition activities of the synthesized compounds were also investigated. Among the synthesized molecules, compound 4 showed the best inhibitory effect against jack bean urease with IC50 values of 0.0036 +/- 0.0010 mu M. (C) 2019 Elsevier B.V. All rights reserved. Recep Tayyip Erdogan Universitesi Research Funding [FBA-2017-788] This study was supported by Recep Tayyip Erdogan Universitesi Research Funding -(Project no FBA-2017-788).

The phthalonitrile (3) including 2-(methoxymethyl)-2,3-dihydro-1,4-benzodioxane substituent and peripherally tetra substituted metal-free (4), zinc(II) (5) and magnesium(II) (6) phthalocyanines were synthesized. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation) properties of phthalocyanines (4-6) were examined in DMSO solutions. The zinc(II) phthalocyanine (5) showed higher singlet oxygen quantum yield (ΦΔ=0.82) compared to metal-free (4) (ΦΔ=0.13) and magnesium(II) (5) (ΦΔ=0.29) phthalocyanine. Also, the fluorescence quenching behaviors of phthalocyanines (4-6) by 1,4-benzoquinone (BQ) were investigated.

In this study, new metal-free and metallo-phthalocyanine complexes (Co, TiO) were synthesized using a piperazine-substituted phthalonitrile derivative. All proposed structures were supported by instrumental methods. Electrochemical studies of H 2 -Pc, Ti IV OPc, and Co II Pc were examined using cyclic voltammetry (CV) and square-wave voltammetry (SWV) techniques. Voltammetric analyses of phthalocyanines supported the proposed structure of the synthesized complexes. All studied phthalocyanines were oxidatively electropolymerized on the working electrode during the repetitive anodic potential scans.

The synthesis and characterization of novel 1,2,4-triazole derivative ( 3 ), nitrile compound ( 5 ) and peripherally tetra 1,2,4-triazole substituted metal-free ( 6 ), zinc(II) (7) , nickel(II) ( 8 ), cobalt(II) ( 7 ), lead(II) ( 9 ) and copper(II) ( 10 ) phthalocyanines were accomplished for the first time. Electrochemical characterization of the complexes were carried out in solution with voltammetric and in situ spectroelectrochemical measurements in different electrolytic systems. Phthalocyanines having redox inactive centers (H + , Zn +2 , Cu +2 , and Ni +2 ) illustrated similar phthalocyanine based electron transfer processes. Redox peaks of these complexes shift slightly due to the different effective nuclear charge of the ions in the core of phthalocyanine ring. The easiest reducible one is the metal free phthalocyanine due to the highest effective nuclear charge of H + . Although big size of ion in the core of lead(II) phthalocyanine disturbed the square planar structure of the complex, this phenomena did not considerably influence the redox processes of lead(II) phthalocyanine.

In present study, the novel peripherally [3-methyl-5-oxo-4-(4-phenoxyphenyl)-4,5-dihydro-1H-1,2,4-triazol-1-yl] substituted Zn(II), Cu(II), Co(II) phthalocyanines were synthesized and characterized spectroscopically. The light absorption/emission behavior of the synthesized phthalocyanines were determined by UV-Vis and fluorescence spectroscopy. The fluorescence quantum yields of the novel phthalocyanine Zn(II) complex in different solvents were calculated. Besides, the urease inhibition activities of the novel compounds were investigated. All synthesized phthalocyanines have a superior inhibitory activity on urease enzyme, while novel phthalocyanines Cu(II) showed the best inhibitory effect against jack bean urease with IC50 values of 0.0035 ±0.0010 µM.

In this study, peripherally and non-peripherally tetra substituted water soluble zinc(II) phthalocyanines (5a and 5b) were synthesized and characterized. Their photochemical and ct-DNA binding properties of them were investigated by UV–Vis spectroscopy. DNA cleavage effects of 5a and 5b were examined using supercoiled pBR322 plasmid DNA on agarose gel electrophoresis. In photochemical studies, the singlet oxygen quantum yields of 5a and 5b were found as 0.76 and 0.78, respectively and the photostability ratios of 5a and 5b were found as 82.12% and 85.28%. The Kb values of 5a and 5b were calculated as 2.92 ± (0.20) × 105 and 1.30 ± (0.16) × 106 M−1, respectively. In addition, 5a and 5b had low cleavage effect in dark but they showed significant photocleavage effect against plasmid DNA under light irradiation in the absence and presence of H2O2. The cytotoxic and phototoxic effects of 5b against A549 and HCT-116 cell lines were investigated using MTT cell viability assay. 5b showed significant phototoxic effects at 1, 5 and 10 μM concentrations and under irradiation on A549 and HCT-116 cell lines. These results showed that compound 5b could be used as a photosensitizer agent in PDT applications.

Morpholine bearing phthalonitriles (3a and 3b) and peripherally and non-peripherally tetra substituted TiOPc and CuPc complexes (4a–5b) were prepared. Electrochemical responses of metallo-phthalocyanines were analysed and compared with each other in order to determine the influence of Cu2+ and TiO2+ metal centers and peripherally or non-peripherally substituents of the complexes. While CuPcs illustrated common Pc based reduction processes, TiOPcs showed extraordinary reduction peaks. During the oxidation processes, all complexes were electropolymerizable and metal centers and non-peripherally or peripherally substituents considerably affect electropolymerization processes. However, it was clearly seen that changing the positions of the substituents did not extensively influence the reduction processes.

4-(1-phenoxypropan-2-yloxy)phthalonitrile (3) and peripherally tetra 1-phenoxypropan-2-yloxy substituted zinc(II) (4), cobalt(II) (5) and copper(II) (6) phthalocyanine were prepared. Structural characterization of novel complexes was performed by spectrophotometric measurements. The determination of the redox active or redox inactive metal center effect on the electrochemistry, in-situ spectroelectrochemisty and electrocolorimetry of compounds were performed in dimethylformamide. The redox properties and mechanisms were examined by electrochemical measurements. The peripherally tetra substituted cobalt(II) phthalocyanine (5) showed both metal and ligand-based redox processes, while zinc(II) (4) and cobalt(II) phthalocyanines only displayed ligand-based redox processes. These results were confirmed by electrochemical and in-situ spectroelectrochemical measurements. Moreover, the semiconducting nature of the compounds were illuminated via electrochemical measurements.

4-(4,5-Diphenyl-4H-1,2,4-triazol-3-ylthio)phthalonitrile (3) and its non-peripherally tetra substituted zinc(II) phthalocyanine (4) and magnesium(II) phthalocyanine (5) derivatives were prepared. The novel compounds 3–5 were characterized spectroscopically. To determine the photodynamic therapy potential of 4 and 5, their photophysical and photochemical properties were investigated. The magnesium(II) phthalocyanine (5) showed the highest fluorescence quantum yield. In addition, non-peripheral substitution of the 4-(4,5-diphenyl-4H-1,2,4-triazol-3-ylthio) groups on the phthalocyanine ring did not affect the fluorescence properties of the phthalocyanines. The zinc(II) phthalocyanine (4) exhibited the highest singlet oxygen quantum yield value. The 4 and 5 exhibited lower photostability than Std-ZnPc. These results show that the zinc(II) phthalocyanine (4) can be used in photodynamic therapy applications with its singlet oxygen production and photostability.

The novel axially chalcone bearing furan or thiphene groups substituted silicon (IV) phthalocyanine complexes were synthesized in this study. These novel phthalocyanines were characterized by general spectroscopic methods such as FT-IR, 1H NMR, UV–Vis, and MALDI-TOF. The aggregation behaviours of the synthesized phthalocyanines were investigated in different solvents and at different concentrations by UV–Vis spectroscopy. The aggregation behavior of the synthesized phthalocyanines were studied at different concentration and different solvents and it was observed chloroform and tetrahydrofuran solutions of furan substituted phthalocyanine (3a) show J-type aggregation as unusual. The photophysical and photochemical properties of the synthesized silicon(IV) phthalocyanine complexes were investigated in dimethylformamide (DMF). It was observed that although both of fluorescent and singlet oxygen quantum yields of the compounds were similar, thiophene substituted phthalocyanine Si(IV) complex show higher quantum yield (3b) than that of furan substituted (3a).

AKCAY, Hakki Turker/0000-0002-8502-9608 WOS: 000451645700027 The structure of the 4-[(4-ethyl-5-phenyl-4H-1,2,4-triazol-3-yl)sulfanyl]phthalonitrile titled molecule is determined by means of X-ray diffraction. The title compound has weak inter- and intramolecular C-H...N-type hydrogen bonds. Furthermore, there is a - interaction between triazole and phenyl rings. Recep Tayyip Erdogan UniversityRecep Tayyip Erdogan University [2014.101.16.01] This study was supported by Recep Tayyip Erdogan University - Research Funding - (Project no 2014.101.16.01).

The synthesis and characterization of novel tetrakis N-(3,5-dichlorophenyl)-5-methyl-3H-1,2,4-triazol-3-one (1) and N-(3,5-dichlorophenyl)-5-ethyl-3H-1,2,4-triazol-3-one (2) substituted phthalonitrile derivatives and their new organosoluble peripherally tetra-substituted zinc(II) (6 and 7) and magnesium(II) (8 and 9) phthalocyanines were studied in this study. Photophysical and photochemical data of these compounds were measured in dimethysulfoxide (DMSO). The magnesium(II) phthalocyanine derivatives showed excellent fluorescent properties and the corresponding zinc(II) phthalocyanines generated efficient singlet oxygen. The fluorescence quenching behavior of the studied tetra-peripherally substituted zinc(II) and magnesium(II) phthalocyanine compounds by the addition of 1,4-benzoquinone were also studied in DMSO. These molecules can distinctly be employed in the field of photodynamic therapy in combination with fluorescence imaging.

The synthesis and characterization of peripherally tetra 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenoxy substituted metal-free (4), zinc(II) (5), oxotitanium(IV) (6), lead(II) (7), nickel(II) (8), copper(II) (9) and cobalt(II) (10) were described for the first time in this study. The photophysical and photochemical properties of metal-free (4), zinc(II) (5), oxotitanium(IV) (6) and lead(II) (7) phthalocyanines were investigated in toluene. The synthesized nickel(II) (8), copper(II) (9) and cobalt(II) (10) phthalocyanines were not evaluated for this purpose because of paramagnetic behavior of the central transition metals in the cavity for these complexes. General trends were described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes of these compounds in toluene. The influence of the variety of central metal ions in phthalocyanine cavity on the spectroscopic, photophysical and photochemical properties were also determined. The fluorescence quenching behavior of the studied peripherally tetra 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenoxy substituted metal-free (4), zinc(II) (5), oxotitanium(IV) (6) and lead(II) (7) by the addition of 1,4-benzoquinone were also studied.

AKCAY, Hakki Turker/0000-0002-8502-9608; Vazquez-Lopez, Ezequiel M./0000-0002-6012-0931; Hokelek, Tuncer/0000-0002-8602-4382 WOS: 000392794300003 In this study, 4-[(4-methy1-5-pheny1-4H-1,2,4-triazol-3-yl)sulfanyl]benzene-1,2-dicarbonitrile was synthesized and its molecular structure was characterized by means of FT-IR. and X-ray diffraction methods. the crystal is monoclinic and belongs to the P21/n space group. There are three weak intermolecular C-H...N type hydrogen bonds in the molecular structure. the geometrical parameters, vibration frequencies, HOMO LUMO energies, and molecular electrostatic potential (MEP) map of the compound (3) in ground state were calculated by using density functional theory (DFT/B3LYP) with the 6-311G(d) basis set. Calculated geometrical parameters were compared with X-ray diffraction geometric parameters. on the other hand, theoretical and experimental FT-IR results were also compared. Higher Education Council The author would like to thank the Higher Education Council for supporting this study within international research.

The new phthalodinitrile containing azine-bridged (3) was prepared by the reaction of 4-nitrophthalonitrile (2) and 4,4′-(1E,1'E)-hydrazine-1,2-diylidenebis(methan-1-yl-1-ylidene)diphenol (1). The new binuclear asymmetric type zinc(II) (5), oxotitanium(IV) (6), tin(II) (7), cobalt(II) (8), copper(II) (9) and nickel(II) (10) phthalocyanine complexes containing azine moiety were synthesized by the cyclotetramerization of azine containing phthalonitrile (3) and unsubstituted phthalonitrile (4). The aggregation behaviors of these compounds were investigated at different concentrations in dimethylsulfoxide (DMSO). Furthermore, the photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen and photodegradation quantum yields) were studied for zinc(II) (5), oxotitanium(IV) (6) and tin(II) (7) phthalocyanine complexes in DMSO. The synthesized cobalt (8), copper (9) and nickel (10) phthalocyanine complexes were not evaluated for this purpose due to transition metal and paramagnetic behavior of central metals in the phthalocyanine cavity.

Compound (3) was synthesized by the reaction of 4-(4,5-diphenyl-1H-imidazol-2-yl) phenol and 4-nitrophthalonitrile in dry DMF in presence of K2CO3 and obtained as single crystal form suitable for x-ray analysis. Vibrational assignments and electronic transitions of the compound (3) were calculated and compared with the experimental results. Compound (4) was obtained from compound (33), by heating at 160 °C for 24 h under N2 atmosphere in dry N,N dimethyl aminoethanol. Compounds (5–8) were synthesized by the same method applied for the synthesis of compound (4) with addition of the corresponding metal salts (ZnCH3COO2, NiCl2, CoCl2, CuCl2). Prepared phthalocyanines were purified by column chromotography using appropriate solvent system and characterized by elemental analysis 1H NMR, 13C NMR, UV–vis, IR and mass spectra. Aggregation behavior of compound (5) was studied in different solvents and different concentrations in DMSO. In addition, protonation behavior of the compound (5) was investigated in different mixtures of sulfuric acid and DMSO.

The synthesis and characterization of new peripherally tetra-3,5-dimethylpyrazole-1-methoxy substituted metal-free ( 4 ), zinc ( 5 ), nickel ( 6 ), cobalt ( 7 ), copper ( 8 ) and lead ( 9 ) phthalocyanines are described for the first time in this study. The photophysical (fluorescence quantum yields and fluorescence lifetimes) and photochemical (photodegradation and singlet oxygen quantum yields) properties of metal-free ( 4 ), zinc ( 5 ) and lead ( 9 ) phthalocyanines are studied in dimethylsulfoxide (DMSO). Nickel ( 6 ), cobalt ( 7 ) and copper ( 8 ) phthalocyanines ( 6–8 ) did not evaluate for this purpose due to transition metal and paramagnetic behavior of central metals in the phthalocyanine cavity. The fluorescence quenching behavior of metal-free ( 4 ), zinc ( 5 ) and lead ( 9 ) phthalocyanines are also investigated. The fluorescence emissions of these phthalocyanines are effectively quenched by 1,4-benzoquinone in DMSO.

The synthesis and characterization of novel peripherally tetra [1,2,4]-triazole substituted metal-free phthalocyanine and its metal complexes (Zn(II), Ni(II), Pb(II), Cu(II) and Fe(II)) and the investigation of electrochemical and spectroelectrochemical properties of metal-free, Zn(II), Pb(II), Fe(II) phthalocyanines were performed for the first time in this study. Electrochemical characterizations of the complexes were performed with voltammetric and in situ spectroelectrochemical measurements. Voltammetric responses of the complexes supported the proposed structures, since complexes bearing redox inactive Pc ring metal centers just gave Pc based electron transfer reactions, while iron phthalocyanine went to metal based electron transfer reaction in addition to the Pc based ones. Electron withdrawing nature of [1,2,4]-triazole substituents shifted the redox processes toward the positive potentials. All complexes were electropolymerized during the oxidation reactions in dichloromethane (DCM) solvent. Types of the metal center of the complexes altered the electropolymerization reactions of the complexes. Spectra and colors of the electrogenerated redox species of the complexes were also determined with in situ spectroelectrochemical and in situ electrocolorimetric measurements.

In this study, novel phthalonitrile derivative (3) was synthesized by the reaction between 4-nitrophthalonitrile (2) and a triazole derivative (1) containing pyridine moiety. Crystal structure of compound (3) was characterized by X-ray diffraction. New metal free and metallo-phthalocyanine complexes (Zn, Cu, and Mg) were synthesized using the phthalonitrile derivative (3). Cationic derivatives of these phthalocyanines (5, 7, 9, and 11) were prepared from the non-ionic phthalocyanines (4, 6, 8, and 10). All proposed structures were supported by instrumental methods. The aggregation behaviors of the phthalocyanines (4-11) were investigated in different solvents such as dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), chloroform and water. Water soluble cationic Pcs (5, 7, 9, and 11) aggregated in water and sodium dodecyl sulfate was used to prevent the aggregation. The second derivatives of the UV-Vis spectra of aggregated Pcs were used for analyzing the Q and B bands of aggregated species. Thermal behaviors of the phthalocyanines were also studied. In addition, anti-bacterial properties of the phthalocyanines were investigated. We used four gram negative and two gram positive bacteria to determine antibacterial activity of these compounds. Compound 7 has the best activity against the all bacteria with 125μg/mL of MIC value. Compounds 4, 6, and 10 have the similar effect on the bacteria with 250μg/mL of MIC value.

In this paper, computational studies were carried out on anastrozole and letrozole, chemotherapy drugs used against breast cancer. Optimization and frequency calculations were performed at B3LYP/6–31G (d) basis set and vibrational frequencies were assignment. Single point calculations were performed at DFT method with a hybrid functional B3LYP/6–311G (d, p) basis set. Theoretical NMR data were obtained at DFT method with a hybrid functional B3LYP/6–311G++ (2d, p) with GIAO (Gauge-Independent Atomic Orbital). IEF-PCM method was used as solvation model. NBO calculations were performed by the same basis set and calculation method with single point calculation. Global and localized reactivity parameters; fukui indices ( f ) chemical hardness ( η ), softness ( S ), chemical potential ( μ ), electronegativity ( χ ) and electrophilicity index ( ω ) were calculated. All computational parameters were compared with the experimental results obtained from the literature.

The molecular structure of the substituted phthalonitrile was analyzed crystallographically and compared with optimized geometric structure. The structural properties of the compound such as energy, vibrational frequency, ground state transitions, 1H and 13C NMR chemical shifts, NBO analysis and hyperpolarizability were computed by DFT (Density Functional Theory) method and compared with experimental results. The novel Mg(II) and Sn(II) phthalocyanines synthesized from the substituted phthalonitrile and their aggregation behaviors were investigated in different solvents and at different concentrations in DMSO.