Phthalocyanine Complexes Research Articles

The role of spacer heteroatomic fragment in spectroscopic and luminescent behaviour of phenyl-substituted phthalocyanine complexes

Peripheral phenyl-substituted metal phthalocyanines with thio and oxa substitution in the spacer bridge fragment were obtained in the work. Spectroscopic properties were studied for the obtained complexes, and the main patterns of behavior and characteristics change depending on the solvent and the nature of the spacer atom. It is shown that the replacement of an oxygen atom in the bridge fragment of a peripheral substituent with a sulfur atom leads to a change in the values of the fluorescence quantum yields. It was revealed that the presence of a spacer fragment is one of the key factors that strongly influence both the solubility of phthalocyanine complexes and their aggregation behavior in various solvents.

Synthesis and some properties of magnesium and zinc tetra-3-(4-bromophenoxy)phthalocyanines

The work describes the synthesis of non-periphery substituted Zn(II), Mg(II) phthalocyanines complexes obtained from 3-(4-bromophenoxy)phthalonitrile. The influence of the metal complex on the spectral and acid-base properties of the obtained compounds was shown. The quantum yield and fluorescence lifetime of the synthesized metal complexes were determined.

Quantum Chemical Stability Analysis of Phthalocyanine Metal One-Dimensional Polymers with Bidentate Ligands.

The combination of metal-phthalocyanine complexes and axially coordinated organic molecules into polymer chains presents a significant challenge in the synthesis of hybrid materials. A calculated structure for one-dimensional coordinate polymers with N-donor ligands using ab initio (PM6) and DFT (LanL2Dz) methods is presented. DFT methods have shown that there is a linear, one-dimensional structure without distorted geometry for the two bipyridine ligands. The components of the proposed polymers consist of square-planar Zn complexes of phthalocyanine (PcZn) connected via bridging ligands (L). Electronic properties of the monomer PcZnL of zinc phthalocyanine with bidentate ligands have been analyzed using calculations based on density functional theory (B3LYP6-31G(d,p)). Molecular orbital calculations show that this connection between the metallomacrocycle and the conjugated ligand results in a small energy gap, promising molecularly active materials as conductors. The crystallographic reports indicate that obtaining this kind of polymer with the participation of Pc Zn and bidentate ligands is possible.

Combining Solid FePc Immobilized on Py-Functionalized Carbon Matrix with Soluble Redox Mediator FePc As an Efficient Cathode Catalyst for Non-Aqueous Li-O2 Batteries

It is important to develop bifunctional catalysts with high activity and stability for reversible oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs) in lithium-oxygen (Li-O2) batteries. Recently, the iron phthalocyanine (FePc) complex has been considered a promising candidate for bifunctional (ORR/OER) O2 catalysts due to its low cost, high catalytic properties, and ease of preparation. In this work, two different structural types of FePc-based solution-phase catalysts as soluble redox mediators (SRMs) and solid FePc immobilized on pyridine-functional carbon supports (multi-walled carbon nanotube, MWCNT and graphene, GR) are investigated to evaluate the influence of FePc structural design on their catalytic activity and kinetics.Our work demonstrated that FePc(solid)/Py/MWCNT exhibited better bifunctional catalytic activity than FePc(solid)/Py/GR in the same electrolyte because of the stronger axial bonding between FePc(solid) and Py/MWCNT. The combination of FePc(solid)/Py/MWCNT and FePc(sol) displays the best cyclability, which can be attributed to the highly efficient solid-liquid interface. Moreover, FePc(solid)/Py/MWCNT without FePc(sol) shows the lowest overpotential owing to the surface-grown thin film Li2O2 is structurally less order than the solution-grown toroidal Li2O2.

Polymer Tetrabenzimidazole Aluminum Phthalocyanine Complex with Carbon Nanotubes: A Promising Approach for Boosting Lithium-Ion Battery Anode Performance

Polymer Tetrabenzimidazole Aluminum Phthalocyanine Complex with Carbon Nanotubes: A Promising Approach for Boosting Lithium-Ion Battery Anode Performance

Ambipolar Heterojunction Sensors: Another Way to Detect Polluting Gases.

Gas sensors based on ambipolar materials offer significant advantages in reducing the size of the analytical system and enhancing its efficiency. Here, bilayer heterojunction devices are constructed using different octafluorinated phthalocyanine complexes, with Zn and Co as metal centers, combined with a lutetium bisphthalocyanine complex (LuPc2). Stable p-type behavior is observed for the ZnF8Pc/LuPc2 device under both electron-donating (NH3) and -oxidizing (NO2 and O3) gaseous species, while the CoF8Pc/LuPc2 device exhibits n-type behavior under reducing gases and p-type behavior under oxidizing gases. The nature of majority of the charge carriers of Co-based devices varies depending on the nature of target gases, displaying an ambipolar behavior. Both heterojunction devices demonstrate stable and observable response toward all three toxic gases in the sub-ppm range. Remarkably, the Co-based device is highly sensitive toward ammonia with a limit of detection (LOD) of 200 ppb, whereas the Zn-based device demonstrates exceptional sensitivity toward oxidizing gases, with excellent LOD values of 4.9 and 0.75 ppb toward NO2 and O3, respectively, which makes it one of the most effective organic heterojunction sensors reported so far for oxidizing gases.

Cycloaddition of natural epoxide and CO2 with the help of multi-nuclear phthalocyanine complexes attached to FPS as a nanosaramic

This study introduces a three-dimensional, densely packed amide polyphthalocyaninezinc, supported by fibrous phosphosilicate (FPS), for the first time (referred to as Complex@Zn-IL/FPS). The XPS and EDX images confirmed that the Complex@Zn-IL nanosaramic was evenly distributed on the FPS’s surface. The cycloaddition reaction from CO2 and natural epoxide using Complex@Zn-IL/FPS nanosaramic as catalysts was reported. Furthermore, the catalyst’s structural heterogeneity was examined using various methods, including SEM, FT-IR, XPS, TEM, and TGA. There was no evidence of zinc leaching into the fluid. In addition, hot filtration provided a comprehensive understanding of the catalyst’s heterogeneous nature. The catalyst’s practical and straightforward reusability was noted after the reaction was completed.

Manganese (III) phthalocyanine complex nanoassembly: Oxygen-Independent generation of superoxide radicals and singlet oxygen for ultrasound-augmented chemodynamic therapy

Singlet oxygen (1O2), an excellent reactive oxygen species (ROS) for tumor therapy, has garnered significant attention recently. However, its production is hindered by the low oxygen content in solid tumors characterized by hypoxia. Consequently, it is urgent to develop an O2-independent generator. In this study, we present a novel nano-assembly composed of manganese (Ⅲ) phthalocyanine complex (MnClPc) encapsulated by human serum albumin (MnClPc@HSA). MnClPc@HSA serves as a conventional sonosensitizer, facilitating the conversion of O2 to 1O2 under ultrasonic stimulation (US). Moreover, MnClPc@HSA enables the conversion of endogenous hydrogen peroxide (H2O2) within tumor to superoxide radical (·O2–) and 1O2 and further enhanced by US. This O2-independent generation of multiple ROS by MnClPc@HSA overcomes the limitations imposed by tumor hypoxia, while inducing immunogenic cell death (ICD) and enhancing the infiltration of T cells as well. When combined with conventional PD-L1 immunotherapy, this approach effectively inhibits the proliferation of distal and lung-metastatic tumors, while concurrently eliminating primary tumors in the bilateral-tumor model of 4 T1 tumor-bearing mice.

Photocatalytic water oxidation by iron and copper phthalocyanine complexes immobilized on Fe3O4@SiO2@TiO2 under visible light irradiation

In this research, the heterogeneous catalysts of Fe3O4@SiO@TiO‐FePc and Fe3O4@SiO@TiO‐ CuPcN (FePc = iron (II) phthalocyanine and CuPcN = copper (II) tetraazaphthalocyanine), termed respectively as nanocomposites 1 and 2, were prepared by immobilizing the FePc and CuPcN complexes on the Fe3O4@SiO@TiO surface and used for the photocatalytic water oxidation reaction. Since phthalocyanine complexes have received very little attention as photocatalysts for water oxidation, the advantage of the synthesized photocatalyst owes to the ability of the phthalocyanine complex grafted on the titanium substrate to oxidize water in the photocatalytic reaction. The prepared nanocomposites were then studied by diffraction (XRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray (EDX), Fourier transform infrared (FT‐IR) spectroscopies, thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), inductively coupled plasma‐optical emission spectroscopy (ICP‐OES), Brunauer–Emmett–Teller (BET) analysis, ultraviolet diffuse reflectance (DRS), and photoluminescence (PL) spectroscopies. The photocatalytic response of water oxidation by nanocomposites 1 and 2 was investigated in the presence of silver nitrate as an electron recipient at ambient temperature. The progress of the water oxidation reaction was monitored with an oxygen meter. The amount of oxygen generated in the presence of nanocomposites 1 and 2 under visible light irradiation was found to be 2.6 and 2.1 mg L−1, respectively. Owing to the existence of magnetic material, these nanocomposites can be effortlessly removed from the response medium with an external magnet. The involved nanocomposites can be used up to three times in catalytic water oxidation reactions with no significant change in their photocatalytic activity.

Application of phthalocyanine complexes of Cu(II), Co(II), Ni(II), and Zn(II) as catalysts in the transfer hydrogenation of acetophenone and its derivatives

In this study, tetra substituted metallophthalocyanines (M: Ni, Zn, Co, and Cu) containing imine and azo groups were synthesized using microwave irradiation. The structures of all complexes have been totally characterized via 1HNMR , 13CNMR , TGA/DTA, LC-MS/MS, elemental analysis, UV–Vis, FT-IR spectroscopy. The comparison of the catalytic features of phthalocyanine based on metals is also discussed briefly. These phthalocyanine-complexes were also used in the transfer hydrogenation (TH) of acetophenone derivatives in the existence of KOH, utilizing isoPrOH as a hydrogen source. Acetophenone compounds determined a TH of up to 99 % conversion. Copper phthalocyanines were first used as catalysts in transfer hydrogenation reactions. The Cu(II) complexes showed higher catalytic activity, converting up to 97 % at 1.0 mol% catalyst loading. Furthermore, we have discovered that the catalytic characteristics of this class of molecules are significantly influenced by both steric and electronic variables.

A novel electrospun polyvinyl alcohol/Co3O4/copper phthalocyanine nanofiber for oxidation of alcohols

That’s a very interesting application of the cobalt oxide modified with copper phthalocyanine complex (II) tetrasodium tetrasulfonic acid (Co3O4/CuSPC) that was produced from Sesbania sesban plant. It’s impressive that the Co3O4/CuSPC was deposited on polyvinyl alcohol (PVA) using a conventional single nozzle electrospinning technique to create Co3O4/PVA/CuSPC nanofibers. TEM, SEM, AFM, FT-IR, EDAX, and elemental analysis were used to determine fiber compositional information. Catalytic activities of this novel hetrogenous catalyst was evaluated on the oxidation of alcohols in green strategy. The reactions were performed without the use of solvents with tetra-n butylammonium peroxomonosulfate (TBAO) as a recoverable oxidant. It’s great to hear that The catalyst was recycled for six times making it more economically and environmentally sustainable.

Novel axially di-substituted natural, cationic and zwitter ionic silicon phthalocyanine derivatives: Synthesis, characterization, sono-photochemical properties

This study focuses on investigating the sono-photophysicochemical properties of recently synthesized and characterized di-axially substituted silicon phthalocyanine complexes, incorporating schiff-base groups and zwitter ions, imparting novel features and potential therapeutic applications. Specifically, our research focused on evaluating the suitability of these complexes for photodynamic therapy (PDT), sonodynamic therapy (SDT), and the emerging field of sono-photodynamic therapy (SPDT). The characterization process involved the application of various analytical techniques, including UV–Vis spectroscopy, infrared (FT-IR) spectroscopy, and proton nuclear magnetic resonance (1H NMR) spectroscopy. Experimental results displayed highly promising outcomes, revealing that the synthesized sensitizers exhibited exceptional efficiency in generating reactive oxygen species, a critical attribute necessary for effective therapeutic interventions. This finding significantly contributes to the development of novel therapeutic agents with enhanced photodynamic and sonodynamic properties. Harnessing the power of light and sound simultaneously through sonophotodynamic therapy offers a unique and synergistic approach, potentially amplifying the therapeutic efficacy of these complexes. The combination of sonochemical and photochemical applications produced better results, for the studied compounds, the quaternized complexes (cationic compounds) showed the higher result. Overall, the results suggest that SPDT is a promising combination therapy for cancer treatment.

Synthesis and Characterization of Titanium Nitride-Carbon Composites and Their Use in Lithium-Ion Batteries.

This work focuses on the synthesis of titanium nitride-carbon (TiN-carbon) composites by the thermal decomposition of a titanyl phthalocyanine (TiN(TD)) precursor into TiN. The synthesis of TiN was also performed using the sol-gel method (TiN(SG)) of an alkoxide/urea. The structure and morphology of the TiN-carbon and its precursors were characterized by XRD, FTIR, SEM, TEM, EDS, and XPS. The FTIR results confirmed the presence of the titanium phthalocyanine (TiOPC) complex, while the XRD data corroborated the decomposition of TiOPC into TiN. The resultant TiN exhibited a cubic structure with the FM3-M lattice, aligning with the crystal system of the synthesized TiN via the alkoxide route. The XPS results indicated that the particles synthesized from the thermal decomposition of TiOPC resulted in the formation of TiN-carbon composites. The TiN particles were present as clusters of small spherical particles within the carbon matrix, displaying a porous sponge-like morphology. The proposed thermal decomposition method resulted in the formation of metal nitride composites with high carbon content, which were used as anodes for Li-ion half cells. The TiN-carbon composite anode showed a good specific capacity after 100 cycles at a current density of 100 mAg-1.

Manganese(III) Phthalocyanine Complex Nanoparticle-Loaded Glucose Oxidase to Enhance Tumor Inhibition through Energy Metabolism and Macrophage Polarization.

Elevated levels of reactive oxygen species (ROS) have demonstrated efficacy in eliminating tumor cells by modifying the tumor microenvironment and inducing the polarization of tumor-associated macrophages (TAMs). Nevertheless, the transient nature and limited diffusion distance inherent in ROS present significant challenges in cancer treatment. In response to these limitations, we have developed a nanoparticle (MnClPc-HSA@GOx) that not only inhibits tumor energy metabolism but also facilitates the transition of TAMs from the M2 type (anti-inflammatory type) to the M1 type (proinflammatory type). MnClPc-HSA@GOx comprises a manganese phthalocyanine complex (MnClPc) enveloped in human serum albumin (HSA), with glucose oxidase (GOx) loaded onto MnClPc@HSA nanoparticles. GOx was employed to catalyze the decomposition of glucose to produce H2O2 and gluconic acid. Additionally, in the presence of MnClPc, it catalyzes the conversion of H2O2 into •O2- and 1O2. Results indicate that the nanoparticle effectively impedes the glucose supply to tumor cells and suppresses their energy metabolism. Simultaneously, the ROS-mediated polarization of TAMs induces a shift from M2 to M1 macrophages, resulting in a potent inhibitory effect on tumors. This dual-action strategy holds promising clinical inhibition applications in the treatment of cancer.

Synthesis of zinc phthalocyanine complex containing tetra propanoic acid groups: Electronic properties and inhibitory effects on some metabolic enzymes

In the new study, first the synthesis and characterization of 2, 10, 16, 24-Tetrakis-3-(phenoxy) propanoic acid phthalocyaninato zinc (II)(4) and its starting compound are presented. The aggregation properties of compound (4) were investigated with the UV–visible spectrum, and the excitation and emission properties were investigated with the fluorescence spectra. The new compounds were characterized by IR, UV-visible, Mass and 1H NMR spectroscopy. These 3-(3,4-dicyanophenoxy) propanoic acid (3) and compound (4) had effective inhibition against α-glycosidase, α-amylase, butyrylcholinesterase and acetylcholinesterase. IC50 values were found as 4.21–6.57 µM for AChE, 0.32–1.88 µM for BChE, 47.14–62.07 µM for α-amylase, and 13.41–21.82 µM for α-glycosidase. By molecular docking study, compared to reference compounds (tacrine and acarbose) of compound (4) [-9.25 kcal/mol for AChE; -9.30 kcal/mol for BChE; -6.50 kcal/mol for α-amylase and -8.49 kcal/mol for α-glycosidase seem to be more effective and promising. Drug development for the treatment of diabetes, hyperglycemia, and obesity has as one of its design goals the creation of molecules that are α-amylase and α-glycosidase inhibitors. As a result, compound (4) can have promising anti Alzheimer drug potential and record as novel anti-diabetic inhibitors.

Construction of high-throughput magnetic circular dichroism measurement system and its application to research on magnetic and optical properties of phthalocyanine complexes.

Magnetic circular dichroism (MCD) spectroscopy is a powerful method for evaluating the electronic structure and magnetic and optical properties of molecules. In particular, MCD measurements have been performed on phthalocyanines and porphyrins with various central metal ions, axial ligands, and substituents to elucidate their properties. It is essential to develop a robust high-throughput technique to perform these measurements comprehensively and efficiently. However, MCD spectroscopy requires very high optical quality for each component of the instrument, and even slight cell distortions can impair the baseline flatness. Consequently, when versatility and data quality are important, an optical system designed for a microplate reader is not suitable for the MCD spectrometer. Therefore, in this study, we develop a new magnetic flow-through cell and combine it with an existing CD spectrometer and autosampler to construct a high-throughput system. The effectiveness and performance of this new system are then evaluated. In addition, based on the MCD and absorption spectra of various phthalocyanine complexes, the effects of substituents and solvents on their magnetic and optical properties and the causes of these effects are discussed. The results demonstrate that this system is effective for the evaluation of the physicochemical properties of various phthalocyanine complexes.

Synthesis and spectral properties of mixed-ligand Zr and Hf phthalocyanine complexes with out-of-plane coordinated alkylamino-β-ketoenolate chromophores and decanoate

The development of novel materials based on modification of phthalocyanines is promising for various applications in science, medicine and technology. Here mixed-ligand Zr and Hf phthalocyanine complexes with out-of-plane coordinated alkylamino-β-ketoenolate chromophores and decanoate were synthesized for the first time. Complexes were obtained by one stage reaction of bis(decanoato)zirconium and hafnium phthalocyanines with alkylamino-β-ketoenols that resulted in replacement of only one decanoate ligand with the alkylamino-β-ketoenol. Therefore, mixed-ligand Zr and Hf complexes with two chromophore systems (phthalocyanine and alkylamino-β-ketoenol) were synthesized by using four different alkylamino-β-ketoenols, and their structural characterizations were carried out by using some spectroscopic methods: 1H NMR, UV–Vis, IR and MALDI TOF MS. In the UV–Vis spectra of the obtained complexes, the absorption bands characteristic for phthalocyanine system were observed along with additional absorption band of out-of-plane ligand (in the region 440–480 nm). The fluorescence spectra of investigated compounds are characterized by a maximum at about 690 nm, which corresponds to the emission of the phthalocyanine macrocycle, while the emission of alkylamino-β-ketoenol ligand is not observed.

High Power Density of a Hydrogen Peroxide Fuel Cell Using Cobalt Chlorin Complex Supported on Carbon Nanotubes as a Noncorrosive Anode.

Hydrogen peroxide fuel cells (HPFCs) have attracted much attention due to their simple one-compartment structures and high availability under harsh conditions such as an anaerobic environment; however, catalysis improvement is strongly demanded for both anodes and cathodes in terms of activity and durability. Herein, we report the high catalytic activity of CoII chlorin [CoII(Ch)] for hydrogen peroxide (H2O2) oxidation with a low overpotential (0.21 V) compared to that of the CoII phthalocyanine and CoII porphyrin complexes, which have previously been reported as active anode catalysts. Linear sweep voltammograms and differential pulse voltammograms of the CoII complexes (CoIIL) and the corresponding ligands clearly showed that the CoIIIL species are the active species for H2O2 oxidation. Then, one-compartment HPFCs were constructed with CoII(Ch) supported on multiwalled carbon nanotubes (CNTs) as the anode together with FeII3[CoIII(CN)6]2 supported on CNTs as the cathode. The maximum power density of the HPFCs reached 151 μW cm-2 with an open circuit potential of 0.33 V when the coverage of CNT surfaces with CoII(Ch) exceeded ∼60% at the anode.

Improved Charge Delivery within Covalently Ligated Cobalt Phthalocyanine Electrocatalyst for CO2 Reduction

Cobalt(II) phthalocyanine (CoPc) complexes are some of the most active catalysts for CO2 electroreduction reaction (CO2ERR). However, these organic complexes are non-conductive, thus the CO2ERR rate is hindered by the...

Exploring improved strategies for therapeutic studies and biological activities of novel zinc and indium phthalocyanines.

This study investigates novel zinc and indium phthalocyanines with Schiff base and sulphur moieties, focusing on their potential for cancer therapy and antimicrobial applications. It explores the effectiveness of photochemical and sono-photochemical methods to enhance singlet oxygen production, which is crucial for photodynamic therapy. The synthesized complexes in this study demonstrated high singlet oxygen quantum yields, with D3 (ZnPc) and D4 (InPc) showing ΦΔPDT values of 0.71 and 0.75, and ΦΔSPDT values of 0.91 and 0.94, respectively. Furthermore, the evaluation for biological properties revealed that both D3 and D4 exhibit significant antidiabetic properties, DPPH radical scavenging activity, DNA cleavage, antimicrobial activity, biofilm inhibition, and microbial cell viability impacts, both with and without photodynamic therapy. Notably, D3 and D4 achieved antimicrobial cell viability inhibition rates of 84.67 ± 4.67% and 98.32 ± 5.96%, respectively, showcasing their effectiveness in photodynamic antimicrobial therapy. Overall, the study highlights the potential of these phthalocyanine complexes as advanced photosensitizers, with strong singlet oxygen generation and promising biological activities, paving the way for future therapeutic applications.