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Keywords = metal phthalocyanines

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16 pages, 2496 KiB  
Article
Silicon Nanowires Sensor Modified with Cu (II) Phthalocyanine Derivative for Phosphate Monitoring
by Milaine Jebali, Zina Fredj, Sameh Daboussi, Mounir Ben Ali and Mohamed Hassen
Chemosensors 2025, 13(8), 297; https://doi.org/10.3390/chemosensors13080297 - 9 Aug 2025
Viewed by 319
Abstract
This study reports the development of a highly sensitive electrochemical sensor for phosphate ion detection, utilizing silicon nanowires (SiNWs) as the transducing elements and a novel copper (II) phthalocyanine-acrylate polymer adduct (Cu (II) Pc-PAA) as the functional sensing layer. Silicon nanowires were fabricated [...] Read more.
This study reports the development of a highly sensitive electrochemical sensor for phosphate ion detection, utilizing silicon nanowires (SiNWs) as the transducing elements and a novel copper (II) phthalocyanine-acrylate polymer adduct (Cu (II) Pc-PAA) as the functional sensing layer. Silicon nanowires were fabricated via metal-assisted chemical etching (MACE) with etching durations of 15, 25, 35, 45, and 60 min. The SiNWs etched for 15 min exhibited the highest sensitivity, showing superior electrochemical performance. Functionalized SiNWs were systematically evaluated for phosphate ion (HPO42−) detection over a wide concentration range (10−10 to 10−6 M) using Mott–Schottky measurements. The surface morphology of the SiNWs was thoroughly characterized before and after Cu (II) Pc-PAA layer functionalization. The sensing material was analyzed using contact angle goniometry and scanning electron microscopy (SEM), confirming both its uniform distribution and effective immobilization. The sensor displayed a Nernstian behavior with a sensitivity of 28.25 mV/Decade and an exceptionally low limit of detection (LOD) of 1.5 nM. Furthermore, the capacitive sensor exhibited remarkable selectivity toward phosphate ions, even in the presence of potentially interfering anions such as Cl, NO3, SO42− and ClO4. These results confirm the sensor’s high sensitivity, selectivity, and fast response, underscoring its suitability for environmental phosphate ion monitoring. Full article
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18 pages, 2959 KiB  
Article
Evaluating Performance of Metal-Organic Complexes as Electrodes in Hydrogen Peroxide Fuel Cells
by Faraz Alderson, Raveen Appuhamy and Stephen Andrew Gadsden
Energies 2025, 18(10), 2598; https://doi.org/10.3390/en18102598 - 17 May 2025
Viewed by 371
Abstract
With increasing energy demands, fuel cells are a popular avenue for portability and low waste emissions. Hydrogen fuel cells are popular due to their potential output power and clean waste. However, due to storage and transport concerns, hydrogen peroxide fuel cells are a [...] Read more.
With increasing energy demands, fuel cells are a popular avenue for portability and low waste emissions. Hydrogen fuel cells are popular due to their potential output power and clean waste. However, due to storage and transport concerns, hydrogen peroxide fuel cells are a promising alternative. Although they have a lower output potential compared to hydrogen fuel cells, peroxide can act as both the oxidizing and reducing agent, simplifying the structure of the cell. In addition to reducing the complexity, hydrogen peroxide is stable in liquid form and can be stored in less demanding methods. This paper investigates chelated metals as electrode material for hydrogen peroxide fuel cells. Chelated metal complexes are ring-like structures that form from binding organic or inorganic compounds with metal ions. They are used in medical imaging, water treatment, and as catalysts for reactions. Copper(II) phthalocyanine, phthalocyanine green, poly(copper phthalocyanine), bis(ethylenediamine)copper(II) hydroxide, iron(III) ferrocyanine, graphene oxide decorated with Fe3O4, zinc phthalocyanine, magnesium phthalocyanine, manganese(II) phthalocyanine, cobalt(II) phthalocyanine are investigated as electrode materials for peroxide fuel cells. In this study, the performance of these materials is evaluated using cyclic voltammetry. The voltammograms are compared, as well as observations are made during the materials’ use to measure their effectiveness as electrode material. There has been limited research comparing the use of these chelated metals in the context of hydrogen peroxide fuel cells. Through this research, the goal is to further the viability of hydrogen peroxide fuel cells. Poly(copper phthalocyanine) and graphene oxide doped with iron oxides had strong redox catalytic activity for use in acidic peroxide single-compartment fuel cells, where the poly(copper phthalocyanine) electrode compound generated the highest peak power density of 7.92 mW/cm2 and cell output potential of 0.634 V. Full article
(This article belongs to the Section D: Energy Storage and Application)
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14 pages, 2768 KiB  
Article
Vanadyl Phthalocyanine as a Low-Temperature/Low-Pressure Catalyst for the Conversion of Fructose to Methyl Levulinate
by Juan Luna, Mataz Alcoutlabi, Elizabeth Fletes, Helia Morales and Jason G. Parsons
Molecules 2025, 30(9), 2065; https://doi.org/10.3390/molecules30092065 - 6 May 2025
Viewed by 409
Abstract
In this study, a vanadyl phthalocyanine was synthesized and characterized using XRD, FTIR, and XPS, confirming the successful metalation of the phthalocyanine ring. XRD analysis showed the vanadyl phthalocyanine crystallized in the P-1 crystal lattice, with unit cell parameters a = 12.058 Å, [...] Read more.
In this study, a vanadyl phthalocyanine was synthesized and characterized using XRD, FTIR, and XPS, confirming the successful metalation of the phthalocyanine ring. XRD analysis showed the vanadyl phthalocyanine crystallized in the P-1 crystal lattice, with unit cell parameters a = 12.058 Å, b = 12.598 Å, and c = 8.719 Å, and the lattice angels were 96.203°, 94.941°, and 68.204°. FTIR spectroscopy supported the metalation by the disappearance of the N-H stretch of the non-metalated phthalocyanine. The vanadyl phthalocyanine was tested as a heterogenous catalyst for the conversion of fructose into methyl levulinate in H2SO4–methanol and HCl–methanol systems. The H2SO4–methanol reaction system catalyzed with the vanadyl phthalocyanine, and a zeroth-order rate constant of 1.10 × 10−6 M/s was observed, which was 1.74 times faster than sulfuric acid alone. The HCl–methanol system showed a zeroth-order of reaction with a rate constant of 2.33 × 10−6 M/s, which was 1.3 times faster than the HCl–methanol alone. While the HCl–methanol system showed a faster reaction rate, product distribution favored methyl levulinate formation in the H2SO4–methanol system. The main products identified were methyl levulinate and hepta-2,4-dienoic acid methyl ester, with a minor amount of hydroxymethylfurfural formed. These results suggest that vanadyl phthalocyanine can be effectively used as a catalyst to increase the rate of fructose conversion to methyl levulinate in either H2SO4 or HCl–methanol. Full article
(This article belongs to the Special Issue Research on Heterogeneous Catalysis—2nd Edition)
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16 pages, 5088 KiB  
Article
A Minimal Electronic Nose Based on Graphene Functionalized with Metalated Pyrazinoporphyrazines and Phthalocyanines for Ammonia, Benzene, and Hydrogen Sulfide Discrimination
by Sonia Freddi, Luca Vaghi, Andrea Penoni, Luca Scapinello and Luigi Sangaletti
Chemosensors 2025, 13(5), 165; https://doi.org/10.3390/chemosensors13050165 - 5 May 2025
Viewed by 739
Abstract
The development of electronic noses is, nowadays, essential for several applications, including breath analysis and industrial security. Ammonia, benzene, and hydrogen sulfide are particularly important due to their environmental and health impacts. Here, graphene-based sensors, functionalized with unconventional in-house synthesized zinc and copper [...] Read more.
The development of electronic noses is, nowadays, essential for several applications, including breath analysis and industrial security. Ammonia, benzene, and hydrogen sulfide are particularly important due to their environmental and health impacts. Here, graphene-based sensors, functionalized with unconventional in-house synthesized zinc and copper octyl-pyrazinoporphyrazines and commercially available zinc phthalocyanine, have been prepared. Enhanced solubility given by the octyl chains allowed us to exploit drop-casting as a straightforward functionalization technique. The sensors demonstrated excellent performance for detecting ammonia, benzene, and hydrogen sulfide as a single sensor, with a competitive detection limit and a high sensitivity compared to the state of the art. In particular, functionalization enabled the detection of hydrogen sulfide, for which no response is observed with bare graphene, and lowered the detection limit for all the gases compared to bare graphene. Additionally, the prepared sensors have been assembled into an e-nose that shows promising potentiality to be used for both industrial and medical applications thanks to its excellent discrimination capability of single gases and mixtures. Full article
(This article belongs to the Special Issue Advanced Chemical Sensors for Gas Detection)
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19 pages, 3868 KiB  
Article
Tailoring Metal Phthalocyanine/Graphene Interfaces for Highly Sensitive Gas Sensors
by Daniele Perilli, Alberto Maria Rizzi and Cristiana Di Valentin
Nanomaterials 2025, 15(9), 691; https://doi.org/10.3390/nano15090691 - 3 May 2025
Cited by 1 | Viewed by 632
Abstract
Developing novel gas-sensing materials is critical for overcoming the limitations of current metal oxide semiconductor technologies, which, despite their widely commercial use, require high operating temperatures to achieve optimal performance. In this context, integrating graphene with molecular organic layers provides a promising platform [...] Read more.
Developing novel gas-sensing materials is critical for overcoming the limitations of current metal oxide semiconductor technologies, which, despite their widely commercial use, require high operating temperatures to achieve optimal performance. In this context, integrating graphene with molecular organic layers provides a promising platform for next-generation gas-sensing materials. In this work, we systematically explore the gas-sensing properties of metal phthalocyanine/graphene (MPc/Gr) interfaces using density functional theory calculations. Specifically, we examine the role of different MPcs (FePc, CoPc, NiPc, and CuPc) and Gr doping levels (p-doped, neutral, and n-doped) in the detection of NH3 and NO2 molecules, used as representative electron-donor and -acceptor testing gases, respectively. Our results reveal that a p-doped Gr is necessary for NH3 detection, while the choice of metal cation plays a crucial role in determining sensitivity, following the trend FePc/Gr > CoPc/Gr > NiPc/Gr, with CuPc/Gr exhibiting no response. Remarkably, FePc/Gr demonstrates sensitivity down to the limit of a single NH3 molecule per FePc. Conversely, NO2 detection is possible under both neutral and n-doped Gr, with the strongest response observed for n-doped FePc/Gr and CoPc/Gr. Crucially, we identify the dz2 orbital of the MPc as a key factor in mediating charge transfer between the gas molecule and Gr, governing the electronic interactions that drive the sensing response. These insights provide valuable guidelines for the rational design of high-sensitivity graphene-based gas sensors. Full article
(This article belongs to the Section Theory and Simulation of Nanostructures)
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15 pages, 4061 KiB  
Article
Investigation of Halogenated Metallic Phthalocyanine (InPcCl and F16CuPc)-Based Electrodes and Palm Substrate for Organic Solid-State Supercapacitor Fabrication
by María Elena Sánchez Vergara, Héctor Iván Sánchez Moore and Luis Alberto Cantera-Cantera
Micromachines 2025, 16(4), 455; https://doi.org/10.3390/mi16040455 - 11 Apr 2025
Viewed by 682
Abstract
In this work, we report on the fabrication of a novel Organic Double-Layer Supercapacitor (ODLSC) using recycled palm as the substrate and electrodes based on halogenated indium and copper phthalocyanines. The electrodes were characterized using Reflectance, the Kulbeka–Munk function, and Fluorescence. Finally, their [...] Read more.
In this work, we report on the fabrication of a novel Organic Double-Layer Supercapacitor (ODLSC) using recycled palm as the substrate and electrodes based on halogenated indium and copper phthalocyanines. The electrodes were characterized using Reflectance, the Kulbeka–Munk function, and Fluorescence. Finally, their electrical behavior was evaluated, and the results were compared with those obtained for a more conventional supercapacitor fabricated on polyethylene terephthalate substrate and using indium tin oxide film for electrodes. Based on the experimental measurements of the fabricated ODLSC, the parameter identification of the classical equivalent circuit model was carried out using the Least Squares of Orthogonal Distances (LSOD) algorithm. The results indicated that the palm supercapacitor exhibited behavior more like that of traditional supercapacitors, as the root square mean error (RMSE) values in the model approximation of the experimental data were in the order of 107. Furthermore, the models obtained allowed a determination of the device’s Electrical Impedance Spectroscopy (EIS), revealing that the Palm SC-T1 exhibited capacitive behavior. In contrast, the manufactured Palm SC-T2, PET SC-T1, and PET SC-T2 devices exhibited inductive behavior. All the materials used in this work, such as the substrates, electrodes, separator membranes, and electrolytes, have a high potential to be used in organic supercapacitors. Full article
(This article belongs to the Special Issue Energy Conversion Materials/Devices and Their Applications)
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12 pages, 3560 KiB  
Article
Cinnamomum-Longepaniculatum-Leaves-Based Fe-N Doped Porous Carbon as an Effective Oxygen Reduction Catalyst
by Yashu Li, Nan Wang, Lu Zhao, Xuanhe Liu, Lin Wang, Chengcheng Xie and Jing Li
Molecules 2025, 30(8), 1708; https://doi.org/10.3390/molecules30081708 - 10 Apr 2025
Viewed by 452
Abstract
Developing low-cost, efficient, and scalable non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) remains a critical challenge in the field of energy conversion. Among various candidates, Fe-N-doped carbon materials have garnered attention as promising alternatives to commercial Pt/C catalysts for ORR. In [...] Read more.
Developing low-cost, efficient, and scalable non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) remains a critical challenge in the field of energy conversion. Among various candidates, Fe-N-doped carbon materials have garnered attention as promising alternatives to commercial Pt/C catalysts for ORR. In this study, we report an Fe-N catalyst synthesized by incorporating iron phthalocyanine with Cinnamomum longepaniculatum waste leaves as the carbon source. This catalyst exhibited an excellent four-electron ORR activity and the half-wave potential (E1/2) reaches 0.875 V, which was superior to that of commercial Pt/C (E1/2 = 0.864 V). Additionally, the catalyst exhibits superior methanol tolerance and stability compared to commercial Pt/C. This approach, which utilizes biomass waste for the synthesis of electrocatalysts, not only provides an effective solution for reducing environmental waste but also addresses the issue of sluggish cathodic ORR kinetics in fuel cells, making it suitable for low-cost, large-scale industrial production. Full article
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13 pages, 3888 KiB  
Article
Gas Sensitivity Improvements of Nanowire Hexadecafluorinated Iron Phthalocyanines by Thermal Vacuum Annealing
by Carmen L. Metzler, Soraya Y. Flores, John Cruz Lozada, Jean González, Sebastián Suárez Schmidt, Danilo Barrionuevo, Peter Feng, Wilfredo Otaño, Luis Fonseca and Dalice M. Piñero Cruz
Chemosensors 2025, 13(3), 95; https://doi.org/10.3390/chemosensors13030095 - 7 Mar 2025
Viewed by 1179
Abstract
In the quest for more sensitive gas sensors, researchers have studied how heating the sensors, using UV light, and thermally annealing sensors improve performance. During thermal annealing, the heating process can improve the crystallinity of the material while also increasing the electrode and [...] Read more.
In the quest for more sensitive gas sensors, researchers have studied how heating the sensors, using UV light, and thermally annealing sensors improve performance. During thermal annealing, the heating process can improve the crystallinity of the material while also increasing the electrode and sensing material interactions to create more available active sites and thus improve sensor performance. Hexadecafluorinated iron (II) phthalocyanine (FePcF16) nanowires have high sensitivity towards NH3 selectively, and thermally annealing the NWs after the deposition can further improve the sensing response and recovery. For this reason, the effect of annealing FePcF16 NWs at different temperatures was studied to optimize these systems. In this work, FePcF16 NWs were synthesized using physical vapor deposition (PVD) to deposit on interdigitated electrodes. The NWs were characterized by SEM, EDS, PXRD, FTIR, and Raman spectroscopy to confirm their purity. The sensors were annealed at different temperatures, inserted into a gas sensing chamber, and exposed to 1 ppm NH3 in air, and the electrical current was measured. The results show that the optimized FePcF16 NWs have excellent sensing properties, with a 58% increase in response towards NH3 after a stepwise annealing at 300 °C confirming these systems are good prospective candidates for sensing NH3 at room temperature. Full article
(This article belongs to the Section Nanostructures for Chemical Sensing)
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8 pages, 1536 KiB  
Communication
Electrochemical Studies of Metal Phthalocyanines as Alternative Cathodes for Aqueous Zinc Batteries in “Water-in-Salt” Electrolytes
by Wentao Hou, Andres Eduardo Araujo-Correa, Shen Qiu, Crystal Otero Velez, Yamna D. Acosta-Tejada, Lexis N. Feliz-Hernández, Karilys González-Nieves, Gerardo Morell, Dalice M. Piñero Cruz and Xianyong Wu
Batteries 2025, 11(3), 88; https://doi.org/10.3390/batteries11030088 - 22 Feb 2025
Cited by 2 | Viewed by 1223
Abstract
Aqueous zinc batteries are emerging technologies for energy storage, owing to their high safety, high energy, and low cost. Among them, the development of low-cost and long-cycling cathode materials is of crucial importance. Currently, Zn-ion cathodes are heavily centered on metal-based inorganic materials [...] Read more.
Aqueous zinc batteries are emerging technologies for energy storage, owing to their high safety, high energy, and low cost. Among them, the development of low-cost and long-cycling cathode materials is of crucial importance. Currently, Zn-ion cathodes are heavily centered on metal-based inorganic materials and carbon-based organic materials; however, the metal–organic compounds remain largely overlooked. Herein, we report the electrochemical performance of metal phthalocyanines, a large group of underexplored compounds, as alternative cathode materials for aqueous zinc batteries. We discover that the selection of transition metal plays a vital role in affecting the electrochemical properties. Among them, iron phthalocyanine exhibits the most promising performance, with a reasonable capacity (~60 mAh g−1), a feasible voltage (~1.1 V), and the longest cycling (550 cycles). The optimal performance partly results from the utilization of zinc chloride “water-in-salt” electrolyte, which effectively mitigates material dissolution and enhances battery performance. Consequently, iron phthalocyanine holds promise as an inexpensive and cycle-stable cathode for aqueous zinc batteries. Full article
(This article belongs to the Special Issue Research on Aqueous Rechargeable Batteries—2nd Edition)
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10 pages, 1579 KiB  
Proceeding Paper
Fabrication and Characterization of Perovskite Solar Cells Using Metal Phthalocyanines and Naphthalocyanines
by Atsushi Suzuki, Naoki Ohashi, Takeo Oku, Tomoharu Tachikawa, Tomoya Hasegawa and Sakiko Fukunishi
Eng. Proc. 2025, 87(1), 6; https://doi.org/10.3390/engproc2025087006 - 18 Feb 2025
Viewed by 448
Abstract
Fabrication and characterization based on experimental results for methylammonium lead iodide (MAPbI3) perovskite solar cells using chemical-substituted metal phthalocyanines (MPc) and naphthalocyanines (MNc) as hole-transport materials have been performed to improve conversion efficiency (η) and stability. The purpose of [...] Read more.
Fabrication and characterization based on experimental results for methylammonium lead iodide (MAPbI3) perovskite solar cells using chemical-substituted metal phthalocyanines (MPc) and naphthalocyanines (MNc) as hole-transport materials have been performed to improve conversion efficiency (η) and stability. The purpose of this study was to fabricate and characterize a MAPbI3 perovskite solar cell using t-butyl MPc and MNc as a hole-transporting layer to improve the photovoltaic performance and stability of η. Photovoltaic characteristics, morphology, crystallinity, and electronic structures were characterized in perovskite solar cells using MPc and MNc. The photovoltaic performance of the perovskite solar cell using t-butyl nickel phthalocyanine (NiPc) reached the maximum value of η at 13.4%. Incorporation of NiPc passivated the surface morphology by increasing the crystal grain size and supporting the carrier diffusion while suppressing carrier recombination near the grain boundary in the perovskite layer. Simulation using a SCAPS-1D program predicted the photovoltaic characteristics of the perovskite solar cell using NiPc. The photovoltaic mechanism was discussed on the basis of an energy diagram of the perovskite solar cell. The insertion of NiPc optimized energy levels near the highest occupied molecular orbital of NiPc and the valence band state of MAPbI3, supporting a charge transfer related to short-circuit current density and η. Full article
(This article belongs to the Proceedings of The 5th International Electronic Conference on Applied Sciences)
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28 pages, 7293 KiB  
Article
Integration of p-Type PdPc and n-Type SnZnO into Hybrid Nanofibers Using Simple Chemical Route for Enhancement of Schottky Diode Efficiency
by A. Al-Sayed, Miad Ali Siddiq and Elsayed Elgazzar
Physics 2025, 7(1), 4; https://doi.org/10.3390/physics7010004 - 23 Jan 2025
Viewed by 2428
Abstract
Palladium phthalocyanine (PdPc) and palladium phthalocyanine integrated with tin–zinc oxide (PdPc:SnZnO) were prepared using a simple chemical approach, and their structural and morphological properties were identified using X-ray diffraction, energy dispersive X-ray analysis, scanning electron microscopy, and transmission electron microscopy techniques. The PdPc:SnZnO [...] Read more.
Palladium phthalocyanine (PdPc) and palladium phthalocyanine integrated with tin–zinc oxide (PdPc:SnZnO) were prepared using a simple chemical approach, and their structural and morphological properties were identified using X-ray diffraction, energy dispersive X-ray analysis, scanning electron microscopy, and transmission electron microscopy techniques. The PdPc:SnZnO nanohybrid revealed a polycrystalline structure combining n-type metal oxide SnZnO nanoparticles with p-type organic PdPc molecules. The surface morphology exhibited wrinkled nanofibers decorated with tiny spheres and had a large aspect ratio. The thin film revealed significant optical absorption within the ultraviolet and visible spectra, with narrow band gaps measured at 1.52 eV and 2.60 eV. The electronic characteristics of Al/n-Si/PdPc/Ag and Al/n-Si/PdPc:SnZnO/Ag Schottky diodes were investigated using the current–voltage dependence in both the dark conditions and under illumination. The photodiodes displayed non-ideal behavior with an ideality factor greater than unity. The hybrid diode showed considerably high rectification ratio of 899, quite a low potential barrier, substantial specific photodetectivity, and high enough quantum efficiency, found to be influenced by dopant atoms and the unique topological architecture of the nanohybrid. The capacitance/conductance–voltage dependence measurements revealed the influence of alternative current signals on trapped centers at the interface state, leading to an increase in charge carrier density. Full article
(This article belongs to the Section Applied Physics)
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25 pages, 11855 KiB  
Review
Effective Factors for Optimizing Metallophthalocyanine-Based Optoelectronic Devices: Surface—Molecule Interactions
by Sakineh Akbari Nia, Aleksandra Tomaszowska, Paulina Powroźnik and Maciej Krzywiecki
Molecules 2025, 30(3), 471; https://doi.org/10.3390/molecules30030471 - 22 Jan 2025
Viewed by 1172
Abstract
As a promising structure for fabricating inorganic—organic-based optoelectronic devices, metal—metallophthalocyanine (MPc) hybrid layers are highly important to be considered. The efficient charge injection and transport across the metal/MPc interface are strictly dependent on the precise molecular orientation of the MPcs. Therefore, the efficiency [...] Read more.
As a promising structure for fabricating inorganic—organic-based optoelectronic devices, metal—metallophthalocyanine (MPc) hybrid layers are highly important to be considered. The efficient charge injection and transport across the metal/MPc interface are strictly dependent on the precise molecular orientation of the MPcs. Therefore, the efficiency of MPc-based optoelectronic devices strictly depends on the adsorption and orientation of the organic MPc on the inorganic metal substrate. The current review aims to explore the effect of the terminated atoms or surface atoms as an internal stimulus on molecular adsorption and orientation. Here, we investigate the adsorption of five different phthalocyanine molecules—free-based phthalocyanine (H2Pc), copper phthalocyanine (CuPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), vanadyl phthalocyanine (VOPc)—on three metallic substrates: gold (Au), silver (Ag), and copper (Cu). This topic can guide new researchers to find out how molecular adsorbance and orientation determine the electronic structure by considering the surface–molecule interactions. Full article
(This article belongs to the Section Applied Chemistry)
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13 pages, 5044 KiB  
Article
Photostability of Indium Phthalocyanines in Organic Solvents
by Gabriela Maria Dyrda and Tomasz Pędziński
Colorants 2025, 4(1), 4; https://doi.org/10.3390/colorants4010004 - 20 Jan 2025
Cited by 2 | Viewed by 1259
Abstract
The effects of photochemical reactions induced by UV radiation in solutions of metal phthalocyanines were carried out to determine the factors that might influence the photostability of photosensitized phthalocyanines. Three different indium phthalocyanines, including the diindium triple-decker phthalocyanine, In2Pc3 ( [...] Read more.
The effects of photochemical reactions induced by UV radiation in solutions of metal phthalocyanines were carried out to determine the factors that might influence the photostability of photosensitized phthalocyanines. Three different indium phthalocyanines, including the diindium triple-decker phthalocyanine, In2Pc3 (1), sandwich indium phthalocyanine, InPc2 (2) and iodoindium phthalocyanine, InPcI (3) in benzene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dichloromethane (DCM) and 1-chloronaphtalene, were studied. The rate of decay of absorption is explained by a decomposition reaction that is of first-order kinetics with respect to the phthalocyanine concentration. In general, the presence of ligand I in phthalocyanine InPcI enhances the rate of decomposition. The kinetics of the degradation process proved to depend on the molecular structure of the complex and seems to be controlled by interactions of the macrocycle bridging nitrogen atoms with the solvent molecules. The indium phthalocyanines in benzene displayed the capacity for singlet oxygen generation. Full article
(This article belongs to the Special Issue Feature Papers in Colorant Chemistry)
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11 pages, 3603 KiB  
Article
Electronic Effects in Cobalt Phthalocyanine Catalysts Towards Noble-Metal-Free, Photocatalytic CO2-to-CO Reduction
by Fan Ma, Hong-Wei Lin, Zizi Li, Wen-Jing Li, Jia-Wei Wang and Gangfeng Ouyang
Molecules 2024, 29(21), 4994; https://doi.org/10.3390/molecules29214994 - 22 Oct 2024
Cited by 1 | Viewed by 1995
Abstract
Noble-metal-free CO2 reduction systems based on cobalt phthalocyanine (CoPc) and its derivatives have demonstrated remarkable photocatalytic performances; however, their structure-activity relationship with electronic tuning remains unexplored. Herein, we now provide a systematic study to investigate the electron effects of substituents [...] Read more.
Noble-metal-free CO2 reduction systems based on cobalt phthalocyanine (CoPc) and its derivatives have demonstrated remarkable photocatalytic performances; however, their structure-activity relationship with electronic tuning remains unexplored. Herein, we now provide a systematic study to investigate the electron effects of substituents on the CoPc family in photocatalytic CO2 reduction, where a Cu(I) heteroleptic photosensitizer is utilized. The highest performance can be achieved using cobalt tetracarboxylphthalocyanine in light-driven CO2-to-CO reduction, with a maximum turnover number of 2950 at 450 nm and an outstanding apparent quantum yield of 63.5% at 425 nm, over ten times the activity with the tetra-dimethylamino-substituted CoPc derivative. The favorable electron-withdrawing effects have been further verified by DFT calculations and cyclic voltammetry, which reduces the overpotential required for CO2 reduction and decreases the Gibbs free energy of the catalyst active intermediates, particularly the CO-desorption energetics. Full article
(This article belongs to the Section Inorganic Chemistry)
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10 pages, 930 KiB  
Article
Optical Dynamics of Picosecond Pulse Trains in Aluminum and Zinc Tetracarboxy-Phthalocyanines
by Quan Miao, Erping Sun and Yan Xu
Symmetry 2024, 16(10), 1337; https://doi.org/10.3390/sym16101337 - 10 Oct 2024
Viewed by 819
Abstract
The nonlinear properties and photophysical dynamics of aluminum and zinc tetracarboxy-phthalocyanines (AlPc and ZnPc) were studied using pulse trains of a 532 nm wavelength, which contain 25 subpulses with a 100 ps width and 13 ns spacing. Considering its interaction with long-duration pulses, [...] Read more.
The nonlinear properties and photophysical dynamics of aluminum and zinc tetracarboxy-phthalocyanines (AlPc and ZnPc) were studied using pulse trains of a 532 nm wavelength, which contain 25 subpulses with a 100 ps width and 13 ns spacing. Considering its interaction with long-duration pulses, the energy structure of phthalocyanine could be substituted by a five-level pattern. The nonlinear transmissions of pulse trains in AlPc and ZnPc were simulated by means of equations about the population rate coupled with the paraxial field equation of two-dimensional space. The well-known Crank–Nicholson numerical method was applied to the theoretical simulation. The results demonstrate that both phthalocyanines are efficient as optical limiters. In its low-intensity region, AlPc shows a much better OL effect than ZnPc. But in the region with high intensity, their energy transmittances are nearly the same. The nonlinear transmission of a pulse is susceptible to the state lifetime and cross section of one-photon absorption. Tetracarboxy-phthalocyanines have advantageous photophysical properties for applications in nonlinear optical areas, such as nonlinear optical devices like optical limiters. Adding central metals such as Al and Zn to phthalocyanines could enhance their photodynamic properties, making them potential optical limiters and photosensitizers. Full article
(This article belongs to the Section Physics)
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