Phthalonitrile Derivative Research Articles

Design and synthesis of novel metallophthalocyanines via two step reactions as potential antimicrobial agents starting with new synthesized phthalonitrile derivatives: Complexation, Extraction and antimicrobial studies

Design and synthesis of novel metallophthalocyanines via two step reactions as potential antimicrobial agents starting with new synthesized phthalonitrile derivatives: Complexation, Extraction and antimicrobial studies

Micelles of poly[oligo(ethylene glycol) methacrylate] as delivery vehicles for zinc phthalocyanine photosensitizers

Drug-loaded polymeric micelles have proven to be highly effective carrier systems for the efficient delivery of hydrophobic photosensitizers (PSs) in photodynamic therapy (PDT). This study introduces the micellization potential of poly(oligoethylene glycol methyl ether methacrylate) (pOEGMA) as a novel approach, utilizing the hydrophobic methacrylate segments of pOEGMA to interact with highly hydrophobic zinc phthalocyanine (ZnPc), thereby forming a potential micellar drug carrier system. The ZnPc molecule was synthesized from phthalonitrile derivatives and its fluorescence, photodegradation, and singlet oxygen quantum yields were determined in various solvents. In solvents such as tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide, the ZnPc compound exhibited the requisite photophysical and photochemical properties for PDT applications. The pOEGMA homopolymer was synthesized via reversible addition-fragmentation chain-transfer polymerization, while ZnPc-loaded pOEGMA micelles were prepared using the nanoprecipitation method. Characterization of the pOEGMA, ZnPc, and micelles was conducted using FTIR,1H-NMR, dynamic light scattering, matrix-assisted laser desorption/ionization time-of-flight mass spectrometries, gel permeation chromatography, and transmission electron microscopy. The critical micelle concentration was determined to be 0.027 mg ml-1using fluorescence spectrometry. The drug loading and encapsulation efficiencies of the ZnPc-loaded micelles were calculated to be 0.67% and 0.47%, respectively. Additionally, the release performance of ZnPc from pOEGMA micelles was monitored over a period of nearly 10 d, while the lyophilized micelles exhibited stability for 3 months. Lastly, the ZnPc-loaded micelles were more biocompatible than ZnPc on L929 cell line. The results suggest that the pOEGMA homopolymer possesses the capability to micellize through its methacrylate segments when interacting with highly hydrophobic molecules, presenting a promising avenue for enhancing the delivery efficiency of hydrophobic PSs in PDT. Moreover, it was also deciphered that obtained formulations were highly biocompatible according to cytotoxicity results and could be safely employed as drug delivery systems in further applications.

Biological Performance of Hexadeca-Substituted Metal Phthalocyanine/Reduced Graphene Oxide Nanobioagents.

This study presents a tetra-substituted phthalonitrile derivative, namely, diethyl 2-(3,4-dicyano-2,5-bis(hexyloxy)-6-(4-(trifluoromethoxy)phenoxy)phenyl)malonate (a), cyclotetramerizing in the presence of some metal salts. The resultant hexadeca-substituted metal phthalocyanines [M= Co, Zn, InCl)] (b-d) were used for the modification of reduced graphene oxide for the first time. The effect of the phthalonitrile/metal phthalocyanines on biological features of reduced graphene oxide (rGO) was extensively examined by the investigation of antioxidant, antimicrobial, DNA cleavage, cell viability, and antibiofilm activities of nanobioagents (1-4). The results were compared with those of unmodified rGO (nanobioagent 5), as well. Modification of reduced graphene oxide with the synthesized compounds improved its antioxidant activity. The antioxidant activities of all the tested nanobioagents also enhanced as the concentration increased. The antibacterial activities of all the nanobioagents improved by applying the photodynamic therapeutic (PDT) method. All the phthalonitrile/phthalocyanine-based nanobioagents (especially phthalocyanine-based nanocomposites) exhibited DNA cleavage activities, and complete DNA fragmentation was observed for nanobioagents (1-4) at 200 mg/L. They can be used as potent antimicrobial and antimicrobial photodynamic therapy agents as well as Escherichia coli microbial cell inhibitors. As a result, the prepared nanocomposites can be considered promising candidates for biomedicine.

Effect of Direct Alkyne Substitution on the Photophysical Properties of Two Novel Octasubstituted Zinc Phthalocyanines.

The synthesis of two novel phthalonitrile derivatives (3-4) bearing ethynylcyclohex-1-ene and ethynylcyclohexane groups and two peripherally octa substituted zinc (II) phthalocyanines (5-6) were prepared. The synthesis of phthalonitrile derivatives was performed with Sonagashira coupling reaction by using palladium-catalyzed. The newly synthesized compounds were characterized by using FT-IR, NMR, mass, and UV-Vis absorption spectroscopy techniques. Aggregation studies of 5 and 6 were performed in various organic solvents and different concentrations in tetrahydrofuran (THF). The photophysical studies of the Pcs were performed in THF to determine the effect of the alkyne groups on the fluorescence of the Pc ring. Substances showing fluorescence properties can be used in practical applications such as to create an image in microscopy. Fluorescence quantum yield (ΦF) and fluorescence lifetime (τF) of 5-6 were calculated. The fluorescence quenching studies of 5-6 were performed by adding the different concentrations of 1,4-benzoquinone (BQ) to a constant concentration of the Pcs in THF and it was found that benzoquinone was an effective quencher. The values of the Stern-Volmer constant (Ksv) and quenching constant (kq) of zinc phthalocyanines (5-6) were examined. All obtained results were compared with each other and with unsubstituted zinc Pc compound used as a reference.

Gem-Dibromovinyl phthalonitriles: synthesis, structure elucidation, Hirshfeld surface analysis and energy framework calculations

A series of versatile phthalocyanine precursors, consisting of gem-dibromovinyl phthalonitrile derivatives, were synthesized and characterized by various spectroscopic and X-ray crystallographic techniques.

Cytotoxic Effects of Compounds with a Carbazole Scaffold on Human Brain, Gynecological, and Colon Cancer Cells

AbstractThe effort to develop new anticancer agents with reduced side effects that can overcome chemotherapeutic resistance is one of the most important research areas of medicinal chemistry. In this study, the synthesis of compounds containing carbazole, one of such agents, and their effects on different types of cancer cell lines are presented. Carbazole compound containing alcohol group 1, its phthalonitrile derivative 2 and carbazole disubstituted axial silicon phthalocyanine compound 3 were synthesized for the first time. These compounds were evaluated for cell proliferation, cell cytotoxicity, cell morphology, cell migration, and cell apoptosis on brain cancer cells (A172 and C6), gynecological cancer cells (HeLa and A2780), colon cancer cells (SW620 and HT29), and normal cells (Beas2B, RPE, and HSF). The findings of the cytotoxic and anticancer effects of the compounds were evaluated together 1 was identified as a potent antiproliferative agent (IC50 values of 1 were 29.99–99.5 μg/mL for normal cells and 1.29–33.57 μg/mL for cancer cells) with mild cytotoxicity (% Cytotoxicity of 1 were 10.8–11.7 for normal cells and 13.8–15.9 for cancer cells). The action mechanism of the compounds was related to inhibiting cell migration and triggering cell apoptosis. Overall, 1 and 2 which appears to be an effective pharmaceutical agent, is a potential focus of further preclinical studies.

Synthesis and Characterization of Metal Phthalocyanine Complex Using Substituted 4-Nitrophthalonitrile Ligand

In this research work, four compounds: 4-nitrophthalamide, 4-nitrophthalonitrile and 4-(ciproxy) phthalonitrile and phthalocyanine complex were synthesized. The synthesis began with the nitration in the position 4 of phthalamide which led to the formation of 4-nitrophthalamide. Dehydration by the thionyl chloride in N,N-dimethylformamide (DMF) led to the formation of 4-nitrophthalonitrile and further reaction of ciprofloxacin with 4-nitrophthalonitrile in DMF forms the phthalonitrile derivative, cyclotetramerization of 4-(ciproxy) phthalonitrile in the presence of nickel salt gave substituted metal phthalocyanine complex. The structures of the synthesized compounds were characterized by NMR, FT-IR spectrophotometry and UV-VIS. Melting point of the compounds ware checked by Griffin MFB-590. The melting points of 4-nitrophthalamide and 4-nitrophthalonitrile were found to be 223 oC and 175 oC respectively. Solubility of the compounds was confirmed in some common laboratory solvent (acetone, methanol and DMF). The electronic spectra of nickel phthalocyanine compound in DMF showed intense Q absorption at 690 nm. The thermal stability of the phthalocyanine derivatives was checked by TGA; the phthalocyanine was heated up to 700 oC to determine the degradation temperature. The temperatures at which the phthalocyanine began to exhibit weight loss was 309 oC. It could, therefore, be concluded that the metal phthalocyanines prepared in this study showed suitably high thermal stability and can be used for further analysis.

A New Soluble Copper Phthalocyanine Derivative as a Smart Material

Copper phthalocyanine (CuPc) and its derivatives are considered as candidate materials in many applications. Particularly, easy and sensitive film-forming ability, commercial availability, chemical stability, and ease in tailoring its molecular structure make CuPc a versatile material. On the other hand, main challenge that Pcs often exhibit is their poor solubility in organic solvents. In this sense, this work involves designing of new CuPc derivatives by introducing suitable substitutions to improve the solubility in organic solvents. Specifically, [2,9,16,23-tetra{(4,5-Diphenyl-1H-imidazole)-2-yl-thio}phthalocyaninato-copper(II)] (1) and [2,9,16,23-tetra{(4,5-Diphenyl-1-methyl-1H-imidazole)-2-yl-thio}phthalocyaninato-copper(II)] (2) were prepared. The results show that compound 1 is soluble in tetrahydrofuran (THF), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), and compound 2 is soluble in chloroform, acetone, methanol, THF, DMF, and DMSO. Optical and spectroscopic properties of the synthesized compounds were also investigated, and it was determined that the energy bang gaps of compounds 1 and 2 are 1.70 eV and 1.56 eV, respectively. Strikingly, we demonstrate that compound 1 is exhibiting a rapid and reversible color change behavior upon altering pH in the entire pH spectrum. As it is known, materials that respond reversibly to chemical and/or physical stimuli in a controllable fashion are regarded as smart materials. Hence, we report that compound 1 is actually a smart material that can be used as a simple yet efficient pH sensor.

Photophysical and photochemical studies on non-peripherally and peripherally Ga(III) chloro phthalocyanines in different solvents

Phthalocyanine compounds display strong absorbance during their interaction with light thanks to the delocalized π bonds. In recent years, the studies have been carried out to use phthalocyanine compounds, which are sensitive to light, as photosensitizers in the singlet oxygen production.In present work, two different phthalonitrile derivatives were separately obtained as a result of the reaction of 3-nitrophthalonitrile and 4-nitrophthalonitrile compounds with 2-hydroxymethyl-1,4-benzodioxane. As a result of the reaction of these phthalonitrile derivatives with gallium(III) metal ion, non-peripherally and peripherally 2-hydroxymethyl-1,4-benzodioxane substituted gallium(III) phthalocyanines (3-GaPc and 4-GaPc) were separately obtained. The synthesis of the compounds was performed by conventional methods and the characterization processes were carried out using ultraviolet and visible light (UV–vis) absorption spectroscopy, infrared (IR) spectroscopy, proton nuclear magnetic resonance (1H NMR ) spectroscopy and matrix assisted laser desorption/ionization mass spectroscopy (MALDI TOF MS) methods. Photophysical, photochemical and aggregation properties of two gallium(III) phthalocyanine compounds were investigated in different solvents such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and toluene solvents for their usability in singlet oxygen generation. Solvents have an effect on the results. The result show that these compound display good solubility and suitable singlet oxygen generation properties in the mentioned solvents.

Phthalocyanine photosensitizers with bathochromic shift, of suitable brightness, capable of producing singlet oxygen with effective efficiency

• New phthalocyanine derivatives as photosensitizers were designed and synthesized. • The phthalocyanines dissolve well in common solvents without aggregation. • The phthalocyanines have improved fluorescence and optical absorption properties. • The phthalocyanines have improved photochemical properties and photostability. • The phthalocyanines can be used as photosensitizers in photocatalytic applications. In this study, novel 3-(2,3-dimethoxyphenoxy)phthalonitrile 2 and its non-peripheral tetra-2,3-dimethoxyphenoxy substituted metal-free phthalocyanine 3 compounds were synthesized. Then, the magnesium(II), zinc(II), and indium(III) acetate phthalocyanine complex derivatives ( 4-6 ) of compound 3 were synthesized using the corresponding metal salts by the template effect. The structures of novel phthalonitrile derivative 2 and its metal-free phthalocyanine compounds 3 as well as different metal-containing phthalocyanine complexes ( 4-6 ) were characterized by elemental analysis, FTIR, UV-vis, 1 H NMR, and MALDI-TOF mass spectroscopic techniques. The phthalocyanines ( 3-6 ) can dissolve well in different polar protic, polar aprotic, and non-polar solvent types without aggregation, with maximum absorption intensity and bathochromic effect. Photophysicochemical properties of the phthalocyanines ( 3-6 ) in dimethyl sulfoxide and important spectral parameter values such as molar extinction coefficient, oscillator strength, and electrical dipole strength were determined, and they were also compared with each other and with their unsubstituted counterparts. It was determined that the phthalocyanines ( 3-6 ) have suitable and sufficient fluorescence quantum yields, fluorescence lifetimes, fluorescence brightness, and other photophysical properties, as well as singlet oxygen generation, phototoxic power, and photostability properties. The phthalocyanines ( 3-6 ), particularly zinc(II) and indium(III) acetate phthalocyanines have remarkable potential for use as Type II photosensitizers for cancer therapy in photodynamic therapy. The phthalocyanines ( 3-6 ) may be promising candidates for various applications as photosensitizers for photodynamic therapy, especially in combination with fluorescent imaging.

A cross-linkable phthalonitrile derivative as a precursor to synthesize nitrogen-doped carbon nanodots for Ni ion detection

A phthalonitrile derivative containing both melamine and benzoxazine moieties has been used as the precursor to prepare luminescent carbon nanodots for Ni ions detection.

Synthesis of isoindole-diimine and its derivatives without ammonia gas bubbling

Isoindole-diimine, which can be obtained by bubbling ammonia gas into a solution of phthalonitrile derivatives in the presence of Na[Formula: see text] ion, is a final and best precursor for phthalocyanine synthesis. In this study, isoindole-diimine and various derivatives have been prepared without bubbling ammonia gas using in situ generated ammonia that was produced from formamide and a strong alkali such as NaOH and NaNH2. A longer reaction time, higher temperature, and larger amount of formamide were required for phthalonitrile derivatives with electron-donating groups, but this method is recommendable in that an NH3 gas cylinder and concomitant gas regulator, which are not inexpensive, are not required. Attempts were made to interpret the IR and absorption spectra of the resultant diimines. The signals due to imino proton or N-H of diimino compounds were experimentally found to appear at around 8.2[Formula: see text]9.5 ppm in 1H-NMR and ca. 3500–3000 cm[Formula: see text] in IR spectra.

Design of N-heterocycle based-phthalonitrile/metal phthalocyanine-silver nanoconjugates for cancer therapies.

This study reports the anticancer properties of carbazole-containing phthalonitrile/phthalocyanine-modified silver nanoparticles for the first time. In this study, a new mono-substituted phthalonitrile namely 3-[9H-carbazole-9-ethoxy]phthalonitrile and its metal phthalocyanines {M = Zn, Co, and Mn(Cl)} were synthesized by template cyclotetramerization of phthalonitrile derivatives. The newly synthesized compounds were characterized using UV-vis, FT-IR, 1H NMR, 13C NMR, and mass spectroscopy. The resultant compounds were successfully linked to the surface of silver nanoparticles. The characterization of the surficial modification was carried out by applying the TEM technique. The cytotoxic activities of the studied nanoconjugates were tested against A549, DLD-1, and Wi38 cell lines by performing a (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) (MTT) assay with/without irradiation. Although the functionalization of silver nanoparticles increased the solubility of phthalocyanines in aqueous media, the presence of phthalonitrile/phthalocyanine derivatives on the silver nanoparticles' surface improved their biological properties. All the studied biological candidates exhibited antiproliferative activities against the cell lines. The IC50 values calculated were between 6.80 and 97.99 μM against the studied cell lines in the dark. However, the IC50 values determined were between 3.11 and 88.90 μM with irradiation. The highest IC50 values obtained were 3.11 and 3.52 μM against the DLD-1 cell line for nanoconjugates 1-AgNP and 3-AgNP, respectively. The findings indicated that the compounds may be utilized as anticancer agents after further studies.

Farklı Kalkon, Ftalonitril ve Periferal Tetra Çinko Ftalosiyanin Türevlerinin In Vitro Layşmanyasidal Aktivitesi

In this study, in vitro leishmanicidal activity of different chalcone compounds (5-8), phthalonitrile derivatives (5a-8a), and zinc phthalocyanine (5b-8b) complexes bearing chalcone compound in peripheral positions were investigated. Phthalonitrile derivatives were obtained in the reaction of 4-nitrophthalonitrile with chalcone compound obtained by the reaction of acetophenone and various aldehydes. Zinc phthalocyanine complexes containing chalcone in the peripheral position were obtained as a result of the reaction of the synthesized phthalonitrile derivative with Zn(CH₃COO)₂ metal salt. The characterization of the synthesized original compounds (8, 8a and 8b) was performed by various spectroscopic methods (IR, 1H and 13C NMR, MALDI-TOF-MS and UV-Vis). Leishmaniasis is a disease lead to by parasites of the genus Leishmania, which can result in death as well as various clinical syndromes, generally in developing countries. New drug studies are needed because the drugs used in the treatment are toxic and resistance develops against them. In this study, the leishmaniacidal activities of synthesized chalcone, phthalonitrile and phthalocyanine series substances against Leishmania infantum and Leishmania major parasites were evaluated for the first time.

New Dyestuff Production to Sensitively Determine the Sealing Capacity of the Implant Abutment Connection

Aim: In this study, it was aimed to synthesize a new dyestuff with fluorescent active properties, which can be easily produced and water-soluble, to be used in sealing tests.
 Materials and Methods:
 The sealing capacities of the implant abutment connection of the dental implant systems manufactured by ESTAŞ were determined spectroscopically by UV-Vis spectrophotometer using the synthesized dyestuff in the first stage. Thanks to the fluorescent active property of the dyestuff, the emission spectra were measured with the fluorescent spectrometer, which is highly sensitive to changes, and the sealing capacities could be determined more precisely, depending on time. In addition, the gap between the implant and the abutment connection was determined using a Scanning Electron Microscope (SEM), and the sealing capacities were evaluated from a different perspective. In addition, sealing tests of the same implant systems were also performed with methylene blue dyestuff and the results were compared. The efficiency of our synthesized dyestuff was determined.
 Results:
 The dyestuff to be used in the sealing tests of the implants was synthesized and characterized in a short time in our laboratory. The phthalocyanine compound from the porphyrin class was obtained as a result of the tetramerization reaction of the synthesized phthalonitrile derivative. The dyestuff, which can be synthesized in a short time like 10 minutes, was purified by taking advantage of the solubility difference and chromatographic methods. The obtained dyestuff was characterized by NMR, FTIR, UV-Vis, and MALDI-TOF MS. The results obtained are in harmony with the structure of the molecule. The dyestuff produced is water soluble and was especially used to determine the sealing capacity of the implant abutment connection of dental implant systems produced by ESTAŞ. The sealing properties of the implant were determined by spectroscopic methods such as UV-Vis and fluorescence. In addition, sealing capacities were evaluated with SEM. According to the results obtained, we can say that the synthesized dyestuff is a dye that can give spectroscopically more sensitive results than methylene blue.
 Conclusions:
 Dental implants, which are artificially placed in the mouth to support dental prostheses, have changed dental treatment methods to a large extent and become the most preferred successful technique. However, infection risks may occur during the treatment due to the formation of a gap between the abutment cap and the implant resulting from both the production and adaptation of the abutment cap, which is a part of the implant. For this reason, it is important that the implants produced are routinely sensitively checked for sealing and put into use. In addition, sealing control will contribute to the control and shaping of the process from the manufacturing stage of the implant.
 In line with all the data obtained, it has been determined that the implant types produced by ESTAŞ have a sealing capacity below the acceptable limits. In addition, it was observed that our newly synthesized dyestuff spectroscopically gave sensitive results in the sealing tests of implant systems.

Hydrogen-bond-driven supramolecular helical assembly of a coumarin-substituted phthalonitrile derivative: synthesis and in vitro anticancer activity against colorectal adenocarcinoma.

Phthalonitrile derivatives are generally reported to crystallize in space groups P21/c and P1 in the literature. In this study, 7-hydroxy-4,8-dimethyl-3-pentylcoumarin (2) and its phthalonitrile derivative (2d) were crystallized; 2d crystallized in the rare trigonal space group R3. In the phthalonitrile derivative (2d), weak C-H...O hydrogen-bonding interactions promoted the formation of supramolecular double helices, and these supramolecular P and M double helices came together to form a honeycomb-like architectural motif involving one-dimensional tubular channels. In silico molecular-docking studies were performed to support the experimental processes and the results agree with each other. In vitro studies of compounds 2 and 2d were performed in LoVo colorectal adenocarcinoma and CCD18Co healthy human cell lines using flow cytometry. For compounds 2 and 2d, there was a statistically significant increase (p < 0.001) in both early and late apoptosis with respect to the control in a dose-dependent manner.

Pyrene Substituted Phthalonitrile Derivative As a Fluorescent Sensor For Detection of Fe3+ Ions in Solutions.

In this current study, the novel bis[4,5-(pyrene-2-yl)-3,6-(hexyloxy)] phthalonitrile (SPN) fluorophore has been successfully synthesized. Structural characterization of this novel compound was performed by different spectroscopic methods such as FT-IR, MALDI-TOF, 1H-NMR, 13C-NMR and elemental analyses as well. In addition, the photophysical properties were determined using UV-vis absorption, steady-state fluorescence, time-resolved fluorescence spectroscopic methods and quantum chemical calculations. The metal sensing behavior of the SPN was determined in the presence of various metals (Li+, Na+, K+, Mg2+, Ca2+, Ba2+, Mn2+, Fe3+, Cr3+, Co2+, Ni2+, Ag+, Cd2+, Al3+, Hg+ and Zn2+) using fluorescence spectroscopy. The novel pyrene based phthalonitrile (SPN) showed high sensitivity and selectivity towards Fe3+ ion over other examined metal ions. In order to perform the determination of Fe3+ ion in environmental samples, experimental conditions such as selectivity, stability, precision, sensitivity, accuracy and recovery were optimized. Also, the complex stoichiometry of the novel pyrene based phthalonitrile (SPN) and Fe3+ ions was determined by a Job's plot. The compound was also studied via density functional theory calculations revealing the interaction mechanism of the molecule with Fe3+ ions.

The effect of the position of the trimethoxy groups as distant substituents on the spectral and acid sensing properties of phthalocyanines

In this study, alpha and beta substituted phthalonitrile derivatives were obtained by using 3,4,5-trimethoxyphenol and 2,4,6-trimethoxyphenol, and metal-free and Co2+ phthalocyanine molecules were synthesized using these starting compounds. After the phthalocyanine compounds were purified and characterized by classical methods, their detailed solubility, UV–Vis and FT-IR spectroscopy studies were performed and it was revealed how the positions of methoxy groups changed the spectroscopic properties of phthalocyanines. In addition, during detailed UV–Vis studies of Pcs, it was determined that alpha-substituted Pcs gave an extra peak in 1 × 10−5 M dichloromethane solution. It was determined that this peak was caused by acid impurities in dichloromethane in trace amounts and UV–Vis spectra in DCM solutions with different trifluoroacetic acid(TFA) concentrations for alpha substituted Pcs (5–8) were studied and their protonation behaviour was examined. It was determined that H2Pc(6) was sensitive to acid even at 1.8 × 10−3 mM concentration. Thus, acid sensor device can be developed by using this Pc molecule, if desired.

Quinoline‐fused both non‐peripheral and peripheral ZnIIand MgIIphthalocyanines: Anti‐cholinesterase, anti‐α‐glucosidase, DNA nuclease, antioxidant activities, and in silico studies

Quinoline‐fused ZnII(ZnPcp/ZnPcnp) and MgII(MgPcp/MgPcnp) phthalocyanines with four 4‐methylquinolin‐2‐ol (1) at non‐peripheral or peripheral positions of the phthalocyanine core have been synthesized via cyclotetramerization of phthalonitrile derivatives (CNp/CNnp) in the presence of zinc (II) and magnesium (II) metal ions in this study. After synthesis and characterization processes, anti‐cholinesterase, anti‐α‐glucosidase, DNA nuclease, antioxidant activities, and in silico calculations of both peripheral and non‐peripheral ZnIIand MgIIphthalocyanines were investigated. The inhibitory effects of metallated phthalocyanines on acetylcholinesterase, butyrylcholinesterase, and α‐glucosidase enzymes were tested by spectrophotometric method. Theoretical methods are used to compare both the chemical and biological activities of the studied phthalonitrile derivatives and metallated phthalocyanine compounds.

Synthesis of V-shaped fused phthalonitriles and control of their molecular orientation

The dibenzo[d,d′′]benzo[1,2-b:4,3-b′]difuran skeleton exhibits a V-shape, which is highly desirable in semi-conductor applications. In this study, we synthesized V-shaped highly fused phthalonitrile derivatives and investigated the use of peripheral substituents to tune the crystal packing of the compounds. The palladium-mediated double C–H activation of 3,6-bis(aryloxy) phthalonitriles afforded 6,7-dicyano-dibenzo[d,d′′]benzo[1,2-b:4,3-b′]difurans. The peripheral substituents affected the packing structure of the single crystals, particularly in the compounds with nBu groups, in which two-dimensional (2D) layered structures were observed. The peripheral substituents also affected the optical properties in the solution, film, and powder states. The layered structure suggested an improvement in the mobilities of organic semiconductors.