Metal Phthalocyanines Research Articles

Review of Yu–Shiba–Rusinov bound state in quantum impurity structures: basic principle and current progress

Abstract Magnetic impurities connected to superconductors reservoir result in bound states within the superconducting gap, so called Yu–Shiba–Rusinov (YSR) state. In the past few years, this field has gained much attention since it is crucial for engineering novel superconducting many-body states, with the perspective of manufacturing Majorana Fermions. The underlying physical picture of YSR state depends closely on the form of the impurities connected to the leads, the manner in which the impurities are organized, and also the diverse local interactions, which is always disclosed with the aid of quantum impurity models. This article provides a comprehensive overview of the progress achieved by previous studies, focusing on the issues demonstrated by quantum impurity structures. The physical mechanisms and the related phenomena assisted by different interactions are discussed in detail. Furthermore, a comprehensive overview of recent experimental achievements is presented, using various metal phthalocyanine molecules as illustrative examples, thereby establishing a robust foundation for future inquiries in this domain.

Synthesis of pegylated metal phthalocyanines, incorporation in hierarchically porous carbon monoliths and evaluation as heterogeneous catalysts

Synthesis of pegylated metal phthalocyanines, incorporation in hierarchically porous carbon monoliths and evaluation as heterogeneous catalysts

Phthalocyanine and metal phthalocyanine are hole transport buffer layers for perovskite solar cell fabrication

This approach allows you to more accurately evaluate the performance of solar panels and identify any prob- lems or degradation in their operation. The LUMO value of mPc closer to the LUMO value of CH3NH3I3PbClx increased conversion energy and short circuit current density (Jsc), which reached a maxi- mum value of 15.97 mA/cm² using the HTL layer of CuPc, and the open circuit voltage (Voc) reached a max- imum at 0.97 V. The change in Jsc corresponds to the fill factor (FF) change. The filling factor (FF) reached a maximum value of 67.35 % when using the HTL layer of CuPc and a minimum value (FF) of 54.23 % when using the HTL layer of H2Pc. The lowest series resistance (R1) and interface resistance (R3) of 11.2 and 39.9 Ohms, respectively, were shown with the HTL layer of CuPc, Capacitive element CPE1 — 305 pF, Ca- pacitive element CPE2 — 0.95 pF. CPE (Constant Phase Element) is an element used in equivalent circuits to describe the non-ideal dielectric properties of materials. The decrease in CPE1 may indicate a decrease in the heterogeneity of the dielectric properties of the perovskite material after coating with different HTL mPc lay- ers. This may be due to changes in structure or mutual actions between layers as a result of exposure to dif- ferences in energy levels.

Modified reverse degree descriptors for combined topological and entropy characterizations of 2D metal organic frameworks: applications in graph energy prediction.

Topological descriptors are widely utilized as graph theoretical measures for evaluating the physicochemical properties of organic frameworks by examining their molecular structures. Our current research validates the usage of topological descriptors in studying frameworks such as metal-butylated hydroxytoluene, NH-substituted coronene transition metal, transition metal-phthalocyanine, and conductive metal-octa amino phthalocyanine. These metal organic frameworks are crucial in nanoscale research for their porosity, adaptability, and conductivity, making them essential for advanced materials and modern technology. In this study, we provide the topological and entropy characterizations of these frameworks by employing robust reverse degree based descriptors, which offer insightful information on structural complexities. This structural information is applied to predict the graph energy of the considered metal organic frameworks using statistical regression models.

A prediction of high temperature magnetic coupling in transition metal phthalocyanines.

In spintronics, a perennial goal has been the generation of organic spin-bearing semiconductor materials with magnetic ordering stable at room temperature. To this end, the class of transition metal phthalocyanines has shown much promise in fulfilling this ambition. In particular, alpha-phase cobalt (II) phthalocyanine (α-CoPc) exhibits strong antiferromagnetic exchange interactions producing a long range order up to ∼100K. However, the underlying mechanism by which this magnetic interaction proceeds is not well understood. In this report, a simple mechanism has been proposed based on the Hubbard Hamiltonian, which elucidates the exchange coupling in α-CoPc. The mechanism provides stipulations for increasing the magnetic coupling, and this directs to a proposal that substitution of the central cobalt ion for rhodium will lead to a significant increase in coupling strength. The strength of this exchange interaction has been evaluated using broken symmetry hybrid exchange density functional theory and indicates that the novel rhodium (II) phthalocyanine system is indeed predicted to exhibit significantly stronger magnetic ordering. This study, therefore, identifies the coupling mechanism in α-CoPc as primarily attributable to kinetic exchange, explains its previously reported strong coupling relative to its first-row transition metal counterparts, and suggests that rhodium (II) phthalocyanine is likely to exhibit stable magnetic ordering at room temperature.

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.

A Minireview on Porphyrin and Phthalocyanine Based Catalysts for Electrocatalytic Synthesis of Ammonia

AbstractAmmonia (NH3) is an important raw material in the chemical industry, but the synthesis of NH3 by the traditional Haber‐Bosch process will increase the carbon footprint. Therefore, it is necessary to develop sustainable routes for NH3 production. New NH3 production schemes, including nitrogen reduction (N2RR), nitrite reduction (NO2RR), and nitrate reduction (NO3RR), have been proposed. Porphyrins and phthalocyanines are macrocyclic compounds with a central metal ion coordinated with nitrogen. The metal centers in these catalysts play a crucial role in binding and activating nitrogen, nitrite, and nitrate. Their unique structure allows for effective electron transfer and catalytic activation in NH3 synthesis. Recently, metal porphyrin and phthalocyanine based catalysts have been demonstrated to be efficient in catalyzing N2RR, NO2RR, and NO3RR. Unfortunately, there is no review focusing on such macrocyclic catalysts for the electrocatalytic synthesis of NH3. In this review, we discuss the electrocatalytic reduction performances and summarize the key factors and reaction mechanisms that affect the catalytic performance of metal porphyrin and phthalocyanine based catalyst systems. This review helps to design more effective new electrocatalysts for NH3 synthesis.

Chitosan-Based Hydrogel Functionalized with Fe(II) Phthalocyanine for Butylated Hydroxyanisole Determination.

The synthesis of functional electrode sensing materials is the key to the construction of electrochemical sensors. A new hydrogel electrode sensing material was developed by incorporating Fe(II) phthalocyanine (FePc) into chitosan-based hydrogels. The chitosan-based hydrogel plays a crucial role in dispersing FePc nanoparticles uniformly and generating a stable environment for the redox reaction of butylated hydroxyanisole (BHA) on the electrode surface. Under optimized conditions, the prepared electrochemical sensor exhibited a detection range of 0.1-30 and 30-1000 μmol/L, with a detection limit of 0.035 μmol/L (S/N = 3). Moreover, this sensor demonstrated exceptional resistance to interference and maintained its stability. These findings suggest that the developed electrochemical sensor is promising for reliable detection of BHA in real samples, highlighting the potential of combining conductive hydrogels with functionalized metal phthalocyanines for accurate and rapid BHA determination.

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.

Efficient electrochemical nitrate reduction by iron phthalocyanine nanorods decorated on multi-walled carbon nanotubes

Electrochemical nitrate reduction reaction (NO3RR) has the dual effect of relieving nitrate contamination and producing the high value-added NH3, which calls for the creation of sophisticated electrodes in order to attain high yield rate, stability, and Faradaic efficiency (FENH3). In this study, iron-based conjugated molecule electrocatalyst, i.e. iron phthalocyanine (FePc), was fabricated into nanorods with excellent crystallinity by a facile precipitation method and applied in NO3RR electrode. The NO3RR performance is enhanced by decorating FePc nanorods on multi-walled carbon nanotubes (CNT) (denoted as FePc@CNT X:10) due to the improved dispersibility and electrical conductivity. The results disclose that FePc@CNT 6:10 exhibits the highest performance with a FENH3 of 94% at −0.45 V (vs. Reversible Hydrogen Electrode) and an ammonia yield rate of 0.35 mmol h−1 mgcat.−1. Notably, a significant NH3 partial current density of approximately 75 mA cm−2 is attained at −0.50 V, correlating with a marginally deteriorated FENH3 of 92.9% and an ammonia yield rate of 0.46 mmol h−1 mgcat.−1. Besides, this catalyst exhibits a long-term NO3RR stability with the ten consecutive cycles. Operando attenuated total reflection surface-enhanced infrared absorptive spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations reveal that NO3− undergoes deoxygenation and extensive hydrogenation steps and FePc is more likely to convert NO3− to NH3 under the ONH route. This work provides advanced insights into the rational design of metal phthalocyanine catalysts for electrocatalytic reactions.

Novel phthalocyanines bearing 1,2,4-triazole substituents linked by sulfur bridges and investigating the photophysical and singlet oxygen generation properties

The new phthalocyanines, H2Pc (4), ZnPc (5), and PbPc (6) linked to 1,2,4-triazole groups were synthesized and characterized. Additionally, the performance of these compounds in photodynamic therapy was investigated. The new metal-free phthalocyanine (H2Pc) (4) was directly obtained from new phthalonitrile (3) without the addition of any metal salt. This original nitrile compound (3) was converted to several new metallic phthalocyanines (Pcs) such as Zn(II) (5), and Pb(II) (6) using appropriate metal salts. Newly prepared phthalocyanines (4–6) were examined for their photodynamic therapeutic (PDT) properties as photosensitizers (PS), yielding significant findings. The structures of these newly obtained compounds were elucidated using spectroscopic techniques such as MALDI-TOF MS, FT-IR, UV–vis, 1H NMR and 13C NMR.

Sulfonic group modifying cobalt (II) phthalocyanine molecule to boost the polysulfide reaction kinetic for high-performance lithium sulfur battery

Metal phthalocyanine have been regarded as an effective additive to restrain the LiPS diffusion process in sulfur cathode to achieve high-performance Li-S battery. Herein, molecular engineering has been used to boost the LiPS adsorption and catalysis abilities of metal phthalocyanine distinctly through a simple sulfonic group grafting strategy. The derived CNT/s-CoPc/S cathode could deliver the initial discharge capacity of 679.8 mAh/g at 1.0 C and no obvious capacity fading even after 500 cycles. The satisfactory electrochemical performance indicates the promising application of CNT/s-CoPc composite as an efficient sulfur carrier. The research presents a successful modification method for the improvement of metal phthalocyanine based additive, contributing to their advancements in Li-S battery furtherly.

Theoretical insights into high-efficiency BaZr0.96Ti0.04S3 chalcogenide perovskite solar cells using phthalocyanine HTLs

In this study, we employed SCAPS-1D simulation to design a novel BaZr0.96Ti0.04S3 chalcogenide perovskite (CP) solar cells (SCs) using metal phthalocyanines (MPc, where M=Cu, Ni, and Zn) HTLs. Through meticulous optimization of the material properties of the absorber and HTLs, we achieved impressive PCEs of 28.93 %, 28.88 %, and 30.12 % for CuPc, NiPc, and ZnPc, respectively. Besides, the optimization increased QE by about 7 % for CuPc and NiPc and ∼ 9 % for ZnPc. Furthermore, generation profiles indicated a significant enhancement in charge carrier production, and Nyquist plots showed higher recombination resistance. These results underscore the promising applicability of MPc in accomplishing high-efficiency BaZr0.96Ti0.04S3 CP SCs.

Synthesis of iron phthalocyanine/CeO2 Z-scheme nanocomposites as efficient photocatalysts for degradation of 2,4-dichlorophenol.

Modulating the photogenerated electrons of CeO2 to activate O2 and efficiently photocatalytic degradation of chlorophenols is a highly desired goal. Herein, we have successfully fabricated an FePc/CeO2 heterojunction through H-bond induced assembly. The photocatalytic degradation of 2,4-DCP by the amount-optimized FePc/CeO2 nanocomposite was improved by 3 times compared with that by pure CeO2. By means of electron paramagnetic resonance (EPR) and single wavelength photocurrent spectroscopy, it is confirmed that the excellent photocatalytic performance is mainly attributed to the formation of the Z-scheme heterojunction, which promotes charge separation and transfer, and the introduction of FePc broadens the visible light absorption range of the heterojunction. Moreover, O2 temperature-programmed-desorbed curves and electrochemical O2 reduction measurement results demonstrate that the single Fe-N4(II) site in FePc is more conducive to promoting O2 activation than that of other metal phthalocyanines. Based on in situ FT-IR and liquid chromatography-tandem mass spectrometry (LC-MS/MS), a possible reaction pathway of 2,4-DCP degradation was proposed. This study provides a novel strategy for preparing CeO2 based Z-scheme heterojunctions with abundant monoatomic sites for pollutant degradation.

Nickel phthalocyanine anchored onto N-doped biochar for efficient electrocatalytic carbon dioxide reduction

Molecular catalysts have been receiving extensive attention due to their explicit, designable, easily modifiable molecular structures and tunable catalytic active sites, which exhibit elegant electrocatalytic performance in electrocatalytic carbon dioxide reduction reactions. However, the susceptibility to aggregation due to strong intermolecular π-π interactions among the metal bipyridines, phthalocyanines and porphyrins among the molecular catalysts limits their catalytic performance. Herein, an active catalyst nickel phthalocyanine anchored N-doped ball milled biochar (NiPc/N-BMBC) was developed with highly enriched pore structure and high surface area for electrocatalytic CO2 reduction reaction. On the nanoscale, NiPc molecules were uniformly anchored on N-BMBC to enhance the dispersion, exposing sufficient catalytic active sites. Concretely, the catalyst NiPc/N-BMBC exhibited extraordinary performance in the electrolytic conversion of CO2 reduction reaction, with a Faredaic efficiency of CO (FECO) > 70 % at an overpotential (−0.75 to −0.95 V vs. RHE) and a high CO partial current density (jCO) of 96 mA cm−2 at −1.0 V vs. RHE, which were much higher than that of NiPc (24 %, 38 mA cm−2) and N-BMBC (9 %, 2 mA cm−2). This work provides a new insight in the structural design of carbon-based electrocatalyst for efficient electrocatalytic CO2 reduction reaction.

Engineering Thin Films of Silicon Phthalocyanines for Organic Thin Film Transistors

Metal phthalocyanines (MPc) show great promise as semiconductors due to their exceptional optoelectronic properties, high thermal and photochemical stability, and ability to be easily synthesized and functionalized for specific applications. The metal/metalloid ion in the center of the MPc ring can significantly influence the electronic, optical, and magnetic properties of the compound, as well as its solubility and stability. The majority of MPc, such as copper phthalocyanine (CuPc) are used as hole-transport materials (p-type) in organic electronics. Silicon phthalocyanines (R2-SiPc) are emerging semiconductors which predominantly moves electrons and have led to high performance n-type organic thin-film transistors (OTFTs). Their low synthetic complexity paired with their versatile axial group facilitates the finetuning of their chemical properties, solution properties and processing characteristics without significantly affecting their frontier orbital levels or their absorption properties. The crystal engineering and film forming characteristics of R2-SiPc semiconductors can be tuned through appropriate axial group functionalization, therefore facilitating their integration into both OTFTs and OPVs by solution processing or vapor deposition.Our group has developed families of R2-SiPc and integrated them into OTFTs with an emphasis on thin film processing and engineering of the interfaces for improved device performance. We have established structure property relationships of the final device performance as a function of 1) R2-SiPc axial groups and peripheral groups, 2) surface chemistry and composition and 3) thin film deposition conditions. I will also be discussing our recent work using advanced film characterization such as polarized Raman microscopy and synchrotron based scanning transmission x-ray microscopy to evaluate the resulting films and optimize the OTFT performance. Figure 1

New phthalocyanine-hybrid glass materials for optoelectronics – Photostability and temperature-dependent optical properties

The organically modified silicate matrix (ORMOSIL) is the most commonly used solution for immobilization of the optically active organic compounds. The materials are characterized by much higher thermal and chemical resistance. The aim of the study was to obtain the hybrid material (in the form of thin films and gels) using the sol-gel method with covalently bound newly synthesized d-block metal phthalocyanine. The hybrid layers were prepared using the dip-coating technique. A series of the sol-gel syntheses based on various types of silicate matrix modifiers (trialkoxysilanes) and their molar ratios were prepared to obtain a photostable and durable material. The optical properties of phthalocyanine (fluorescence) with different concentration in the hybrid glass matrix were studied. Thermoluminescence of the hybrid materials were analyzed. Finally, tests of material stability under the exposure of UV at room temperature and additional under high-energy radiation were carried out with emission measurement in the ultraviolet range and in the temperature range 298–573K.

Modulating the coordination environment and metal choice in carbon buckypapers supported metal phthalocyanines for enhanced electrocatalytic carbon dioxide reduction

In the search of versatile electrocatalysts for the electrochemical reduction of carbon dioxide (CO2RR), different transition metal phthalocyanines (MPc, where M=Fe, Co, Ni and Cu) have been immobilized by an easy and scalable wet impregnation on carbon nanotubes (CNTs) in the form of buckypaper (BP). Both the nature of the metal and the surface chemistry of the carbon support were found to play a pivotal role in determining their CO2RR efficiency and selectivity. We disclose here a potentiodynamic strategy for the controlled surface modification of BP with N- and P-containing polymeric species as a simple heterogenization strategy for molecular catalysts, enabling to easily tune their electrocatalytic performance. Syngas (mixture of H2 and CO) was obtained as the main product from CO2RR using FePc, CoPc and NiPc as electrocatalysts on functionalized (BPf) or non-modified BP. In contrast, CuPc was found to mainly catalyze the hydrogen evolution reaction (HER), with small amounts of formate as the only CO2RR product. It is possible to modulate the H2/CO ratio in the final product through the appropriate selection of the metal in MPc, the modification of the coordination environment by the controlled functionalization of the carbon support and the adjustment of the operating conditions. In particular, H2/CO ratios in a range between 0.17 and 1.28 have been obtained with good stability during electrolysis. Among all the MPc studied, CoPc surfaced as the most promising candidate for the reduction of CO2 to CO and H2 production, a finding substantiated by computational studies highlighting the positive impact of phosphate ligands on CoPc. This strategy outlines the starting line of a potential route toward the controlled generation of CO2RR-related products.

Effects of Metal Phthalocyanine and Naphthalocyanine on Perovskite Solar Cells

Effects of Metal Phthalocyanine and Naphthalocyanine on Perovskite Solar Cells

Air-Stable Wafer-Scale Ferromagnetic Metallo-Carbon Nitride Monolayer.

The pursuit of robust, long-range magnetic ordering in two-dimensional (2D) materials holds immense promise for driving technological advances. However, achieving this goal remains a grand challenge due to enhanced quantum and thermal fluctuations as well as chemical instability in the 2D limit. While magnetic ordering has been realized in atomically thin flakes of transition metal chalcogenides and metal halides, these materials often suffer from air instability. In contrast, 2D carbon-based materials are stable enough, yet the challenge lies in creating a high density of local magnetic moments and controlling their long-range magnetic ordering. Here, we report a novel wafer-scale synthesis of an air-stable metallo-carbon nitride monolayer (MCN, denoted as MN4/CNx), featuring ultradense single magnetic atoms and exhibiting robust room-temperature ferromagnetism. Under low-pressure chemical vapor deposition conditions, thermal dehydrogenation and polymerization of metal phthalocyanine (MPc) on copper foil at elevated temperature generate a substantial number of nitrogen coordination sites for anchoring magnetic single atoms in monolayer MN4/CNx (where M = Fe, Co, and Ni). The incorporation of densely populating MN4 sites into monolayer MCN networks leads to robust ferromagnetism up to room temperature, enabling the observation of anomalous Hall effects with excellent chemical stability. Detailed electronic structure calculations indicate that the presence of high-density metal sites results in the emergence of spin-split d-bands near the Fermi level, causing a favorable long-range ferromagnetic exchange coupling through direct exchange interactions. Our work demonstrates a novel synthesis approach for wafer-scale MCN monolayers with robust room-temperature ferromagnetism and may shed light on practical electronic and spintronic applications.