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Ammonia (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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Developing economical non-platinum oxygen reduction reaction (ORR) catalysts is crucial for the continuous development of fuel cell technology. Transition metal phthalocyanines (TM-Pc) are recognized as ideal catalysts for ORR due to their high turnover frequency and structural tunability. However, the catalytic performance of TM-Pc monolayers with different central atom compositions in ORR has not been sufficiently investigated and explored so far. In this study, a series of TM-Pc monolayers with different central atom compositions were systematically screened to explore their interaction law and catalytic mechanism in ORR based on density functional theory, cleverly using a combination of high-throughput screening and experiment. Our calculations show that the change of the d-band center avoids the strong adsorption of intermediates, and the interaction strength between intermediates and TM-Pc determines the catalytic activities for the ORR. Among the 30 candidate materials, we identified two promising candidates, Fe-Pc and Mn-Pc, which not only have low overpotentials of 0.45 and 0.47 V but also have high thermodynamic and electrochemical stability. The results guide the rational design of high-performance ORR electrocatalysts and are also of reference significance for elucidating the catalytic mechanism of TM-Pc materials for ORR. [Display omitted] • TM-PC electrocatalysts for ORR are systematically screened. • Fe-Pc and Mn-Pc, two highly promising materials, are established. • The ORR mechanism of TM-Pc materials is thoroughly investigated. [ABSTRACT FROM AUTHOR]

The document is the contents list for an issue of the journal Chemical Communications. It includes articles on various topics such as the synthesis of chiral systems, progress in extractants for actinides and lanthanides separation, and the design of sulfonimide anions for rechargeable lithium batteries. The journal is published by The Royal Society of Chemistry and aims to connect the world with the chemical sciences. [Extracted from the article]

Dual‐single‐atom catalysts (DSACs) are the next paradigm shift in single‐atom catalysts because of the enhanced performance brought about by the synergistic effects between adjacent bimetallic pairs. However, there are few methods for synthesizing DSACs with precise bimetallic structures. Herein, a pre‐coordination strategy is proposed to precisely synthesize a library of DSACs. This strategy ensures the selective and effective coordination of two metals via phthalocyanines with specific coordination sites, such as −F− and −OH−. Subsequently, in situ confinement inhibits the migration of metal pairs during high‐temperature pyrolysis, and obtains the DSACs with precisely constructed metal pairs. Despite changing synthetic parameters, including transition metal centers, metal pairs, and spatial geometry, the products exhibit similar atomic metal pairs dispersion properties, demonstrating the universality of the strategy. The pre‐coordination strategy synthesized DSACs shows significant CO2 reduction reaction performance in both flow‐cell and practical rechargeable Zn‐CO2 batteries. This work not only provides new insights into the precise synthesis of DSACs, but also offers guidelines for the accelerated discovery of efficient catalysts. [ABSTRACT FROM AUTHOR]

Modulating the photogenerated electrons of CeO2 to activate O2 and efficiently photocatalytic degra- dation 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 spec- troscopy, it is confirmed that the excellent photocatalytic performance is mainly attributed to the for- mation of the Z-scheme heterojunction, which promotes charge separation and transfer, and the intro- duction of FePc broadens the visible light absorption range of the heterojunction. Moreover, O2 tempera- ture-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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Guided nanowires grown on polymer surfaces facilitate their seamless integration as flexible devices without post‐growth processing steps. However, this is challenging due to the inability of polymer films to provide the required lattice‐matching effect. In this work, this challenge is addressed by replicating highly aligned nanogrooves from a compact disc (CD) onto a casted flexible polydimethylsiloxane (PDMS) surface. Leveraging the replicated nanogrooves, copper hexadecafluorophthalocyanine (F16CuPc) and various metal phthalocyanines are guided into large‐area, self‐aligned nanowires. Subsequently, by employing specifically designed shadow masks during electrode deposition, these nanowires are seamlessly integrated as either a monolithic flexible photodetector with a large sensing area or on‐chip flexible photodetector arrays. The resulting flexible photodetectors exhibit millisecond and long‐term stable response to UV–vis–NIR light. Notably, they demonstrate exceptional bending stability, retaining stable and sensitive photoresponse even at a curvature radius as low as 0.5 cm and after enduring 1000 bending cycles. Furthermore, the photodetector array showcases consistent sensitivity and response speed across the entire array. This work not only proves the viability of guided nanowire growth on flexible polymer surfaces by replicating CD nanogrooves but also underscores the potential for large‐scale monolithic integration of guided nanowires as flexible devices. [ABSTRACT FROM AUTHOR]

Highlights Aramid fiber‐reinforced epoxy resin composites (AFRP) are the main components of electrical equipment such as GIS insulated tie rods, but the poor interfacial bonding between aramid fibers (AF) and epoxy resin (EP) results in a degradation of the material's insulating properties. In this paper, iron phthalocyanine (FePc) molecules are introduced on the AF surface, and the π‐π interaction effect between the metal phthalocyanine rings is used as a driving force to guide the spontaneous assembly of FePc into a three‐dimensional microstructure, and the effect of microstructures with different FePc contents on the insulating properties of AFRP interfaces is investigated. Combining a series of test simulation methods such as surface potential attenuation test, electric tree test, interlayer shear test, and molecular dynamics simulation, reveals the enhancement mechanism of the electrical insulation performance of the interface. The results show that FePc at four contents has an enhancement effect on the flashover voltage along the AF and the breakdown voltage at the AFRP interface, with a maximum enhancement of 25.63% for the flashover voltage and 232.23% for the breakdown voltage. Self‐assembled three‐dimensional structures on aramid surfaces were constructed via iron phthalocyanine molecules. The effects of self‐assembled structures on physicochemical properties are compared. Modifications substantially increase the breakdown voltage and flashover voltage. The mechanism of microstructure on interface breakdown voltage enhancement is revealed. The overall effect of multiple factors on insulation properties is analyzed. [ABSTRACT FROM AUTHOR]

The indiscriminate use of pesticides makes us susceptible to the toxicity of these chemical compounds, which may be present in high quantities in our food. It is crucial to develop inexpensive and rapid methods for determining these pesticides for government control or even for the general population. In this study, we investigated the fabrication of self-assembled LbL films using multi-walled carbon nanotubes (MWCNT) and nickel tetrasulphonated phthalocyanine (NiTsPc) as an electrochemical sensor for the herbicide Diquat (DQ). The Layer-by-Layer (LbL) assembly of the (MWCNT/NiTsPc) film was examined, along with its structural and morphological characteristics. The effect of the number of layers in DQ detection was evaluated by cyclic voltammetry, followed by the detection through differential pulse voltammetry. The achieved limit of detection was 9.62 × 10−7 mol L−1. A ~ 30% decrease in sensitivity was observed in the presence of Paraquat, a banned herbicide and electrochemical interferent due to the structural similarities, which is regularly neglected in the most published studies. The sensor was tested in real samples, demonstrating a recovery of 98.5% in organic apples. [ABSTRACT FROM AUTHOR]

In this work, non-peripherally tetra 3-(4-(4-acetylpiperazin-1-yl)phenoxy) substituted nickel(II) phthalocyanine (NiPc), cobalt(II) phthalocyanine (CoPc), zinc(II) phthalocyanine (ZnPc), copper(II) phthalocyanine (CuPc) and lead(II) phthalocyanine (PbPc) were synthesized. The structural characterization of the novel compounds was performed by a combination of instrumental methods. The electrochemical and in-situ spectroelectrochemical responses of the compounds were recorded and redox properties were illuminated. Graphitic carbon nitride(g-C 3 N 4) was synthesized by thermal decomposition of urea and combined with metallophthalocyanines to avoid agglomeration of phthalocyanine, to obtain homogeneous microstructured catalyst and to provide synergistic effects between pyridinic N-metal bonds of g-C 3 N 4 and metallophthalocyanines (MPcs). The synthesized compounds were electropolymerized onto g-C 3 N 4 thanks to piperazin substitute groups. The oxygen evolution reaction (OER) of g-C 3 N 4 /Poly-MPcs was investigated in alkaline electrolyte (1 M KOH). The g-C 3 N 4 /Poly-NiPc exhibited excellent electrocatalytic performance with low overpotential and Tafel slope, respectively, 380 mV@ 10 mA cm−2 and 80 mVdec−1, which is superior to the g-C 3 N 4. Moreover, g-C 3 N 4 /Poly-NiPc electrocatalyst exhibited ∼100 times higher current density than g-C 3 N 4. [Display omitted] • Non-peripherally tetra 1-(4-(4-hydroxyphenyl) piperazine-1-yl) ethanone substituted MPcs were synthesized. • MPcs were electropolymerized on g-C 3 N 4 nanosheets. • The GCE/g-C 3 N 4 /poly-MPc electrodes were used for OER in alkaline electrolytes. • The g-C 3 N 4 /Poly-NiPc electrocatalyst exhibited a low overpotential of 380 mV at 10 mA cm−2. • g-C 3 N 4 /Poly-NiPc electrocatalyst exhibited ∼100 times higher current density than g-C 3 N 4. [ABSTRACT FROM AUTHOR]

Every year, cancer claims the lives of hundreds of thousands of people, despite the fast advancements in science and technology. Numerous scientific investigations are conducted to create therapeutic approaches that do not have the drawbacks of conventional cancer treatment methods. A novel approach to treating cancer is sono‐photodynamic therapy, which has a far higher therapeutic efficacy than photodynamic therapy. For this purpose, peripherally bis 3‐[(4‐tert‐butylbenzyl)oxy substituted metal and metal‐free phthalocyanines were synthesized and characterized. Additionally, the spectral, aggregation and sonophotochemical properties of these phthalocyanines in DMSO were examined. Metallophthalocyanines to generate singlet oxygen was examined photochemically and sonophotochemically. The findings of the sono‐photochemical experiments showed great promise, showing that the synthesized sensitizers were effective at producing reactive oxygen species for successful therapeutic treatments. The development of innovative therapeutic medicines with improved photodynamic and sonodynamic characteristics is aided by this discovery. Using sonophotodynamic therapy to concurrently harness the power of light and sound is a novel and synergistic technique that may enhance the therapeutic efficacy of these complexes. For the investigated al of compounds, The combination of sonochemical and photochemical applications generated better results. Overall, the findings point to SPDT as a potentially effective combination therapy for the treatment of cancer. [ABSTRACT FROM AUTHOR]

Two series of metallo‐(Zn(II), Mg(II), and Ru(II)) and free‐base phthalocyanines (Pcs) with a carboxyl anchoring group and well‐established bulky peripheral substituents (either tert‐butyl or bulky 2,6‐diisopropylphenoxy) were synthesized and tested as sensitizers in dye‐sensitized solar cells (DSSCs). The trend of photovoltaic efficiencies (PCEs) for free‐base and metallo Pcs followed the order Zn(II)Pc>Mg(II)Pc≫H2Pc ≈ Ru(II)Pc regardless of the peripheral substitution. Higher efficiencies (4.95 versus 3.63 for the Zn(II) derivatives) were achieved with Pcs bearing the bulkier 2,6‐diisopropylphenoxy group, indicating a lower aggregation and more suitable HOMO‐LUMO levels. Furthermore, these derivatives showed a morelevant influence of the metal on the PCE values (from the highest 4.95 for the Zn(II)Pc to the lowest 0.23 for the Ru(II)Pc. In both series, the best PCEs observed with the Zn(II) derivatives were mainly due to their highest Jsc values. The lowest efficiencies found for the free‐bases and Ru(II) derivatives were attributed to a mismatch between their LUMO levels and the conduction band of the TiO2,and lower light‐harvesting capabilities, respectively. In conclusion, Zn(II) derivatives are still the best Pc candidates to use as sensitizers in molecular photovoltaics. [ABSTRACT FROM AUTHOR]

Sulphur compounds and mercaptans in gas condensate cause corrosion problems, poison catalysts in catalytic processes, and have adverse environmental impact through SOx emission upon combustion. Therefore, it is essential to remove sulphur and mercaptan from gas condensate to standard levels. In this study, the oxidative desulphurization (ODS) process in the presence of a cobalt phthalocyanine sulfonamide‐based catalyst was investigated. The homogeneous catalyst containing 23 wt.% active material was used and optimum operating conditions of temperature, volume ratio of caustic to gas condensate, caustic concentration, and solvent amount were determined to decrease sulphur content to less than 500 ppm and mercaptan to less than 200 ppm. The catalyst consumption in all experiments was kept constant at a minimum level (0.01 g/400 mL gas condensate). Results showed that this catalyst improved the reaction rate in the lower temperature and lower caustic to feed ratio and lower caustic concentration. The maximum sulphur removal was obtained at 5°C and 4 vol.% of caustic to gas condensate ratio at 16.7 wt.% of caustic concentration. Moreover, this catalyst improved sulphur removal from the gas condensate to about 5% compared to caustic sweeting without catalyst. Sulphur compounds had higher solubility in acetone rather than methanol, and sulphur removal by acetone was 96% while it was 91% for methanol. Finally, the economical and acceptable solvent for sulfoxides removal was methanol with 5% volume fraction. [ABSTRACT FROM AUTHOR]

[Display omitted] The development of stable and efficient heterojunction photocatalysts for wastewater environmental purification exhibits a significant challenge. Herien, a promising binary heterojunction complex comprising boron subphthalocyanine bromide/bismuth oxychloride (SubPc-Br/BiOCl) was successfully synthesized using the hydrothermal method, which involved the self-assembled of SubPc-Br on the surface of BiOCl via intermolecular π-π stacking interactions to compose an electron-transporting layer. The photocatalytic efficiency of SubPc-Br/BiOCl for the degradation of tetracycline and the minocycline exhibited a substantial improvement of 29.14% and 53.72%, respectively, compared to the original BiOCl. Experimental characterization and theoretical calculations elucidated that the enhanced photocatalytic performance of the SubPc-Br/BiOCl composite photocatalysts stemmed from the S-scheme electron transport mechanism at the interface between BiOCl and SubPc-Br supramolecules, which broadened the visible light absorption range, increased the carrier molecular efficiency, and accelerated the carriers. Furthermore, molecular dynamic (MD) simulations provided insights into the action trajectories of the two semiconductors, revealing that the presence of SubPc-Br enhances the water and organic pollutant adsorption capabilities of the BiOCl surface within the supramolecular array system. In conclusion, the synthesis and analysis of the binary heterojunction complex SubPc-Br/BiOCl yield valuable insights into the efficient photocatalytic degradation of antibiotics, holding great promise for diverse environmental applications. [ABSTRACT FROM AUTHOR]

Although second near‐infrared (NIR‐II, 1000–1500 nm) light has attracted considerable attention, especially for life sciences applications, the development of organic dyes with NIR‐II absorption remains a formidable challenge. Herein we report the design, synthesis, and electronic properties of 20π‐electron antiaromatic benziphthalocyanines (BPcs) that exhibit intense absorption bands in the NIR region. The strong, low‐energy absorption of the antiaromatic BPcs is attributed to electric‐dipole‐allowed HOMO‐LUMO transitions with narrow band gaps, enabled by the reduced structural symmetry of BPc compared with regular porphyrins and phthalocyanines. The combination of peripheral substituents and a central metal decreases the HOMO‐LUMO energy gaps, leading to the extension of the absorption bands into the NIR‐II region (reaching 1100 nm) under reductive conditions. [ABSTRACT FROM AUTHOR]

This study employs density functional theory (DFT) calculations at the B3LYP/6-311+g(d,p) level to investigate the interaction of XH3 gases (X = N, P, As) with the Mn-phthalocyanine molecule (MnPc). Grimme's D3 dispersion correction is applied to consider long-range interactions. The adsorption behavior is explored under the influence of an external static electric field (EF) ranging from −0.514 to 0.514 V/Å. Chemical adsorption of XH3 molecules onto the MnPc molecule is confirmed. The adsorption results in a significant decrease in the energy gap (Eg) of MnPc, indicating the potential alteration of its optical properties. Quantum theory of atoms in molecules (QTAIM) analysis reveals partially covalent bonds between XH3 and MnPc, and the charge density differenc (Δρ) calculations suggest a charge donation-back donation mechanism. The UV-vis spectrum of MnPc experiences a blue shift upon XH3 adsorption, highlighting MnPc's potential as a naked-eye sensor for XH3 molecules. Thermodynamic calculations indicate exothermic interactions, with NH3/MnPc being the most stable complex. The stability of NH3/MnPc decreases with increasing temperature. The direction and magnitude of the applied electric field (EF) play a crucial role in determining the adsorption energy (Eads) for XH3/MnPc complexes. The Eg values decrease with an increasing negative EF, which suggests that the electrical conductivity (σ) and the electrical sensitivity (ΔEg) of the XH3/MnPc complexes are influenced by the magnitude and direction of the applied EF. Overall, this study provides valuable insights into the suggested promising prospects for the utilization of MnPc in sensing applications of XH3 gases. [ABSTRACT FROM AUTHOR]

In the present study, two iron phthalocyanine (FePc)-based nanocatalysts were synthesized and fully characterized. The carbon nanotubes (CNT) functionalized in an easy way with either Fe(II)Pc or Fe(III)Pc exhibit a very good catalytical activity. The activity in real wastewater effluent was comparable with the activity in distilled water. The procedure of modeling and optimizing with the assistance of chemometrics, utilizing design of experiments (DOE) and response surface methodology (RSM), revealed the conditions of optimum for decaying Reactive Yellow 84 on the nanocatalysts FePc_CNT. These optimal conditions included a catalyst dose of 1.70 g/L and an initial concentration (C0) of 20.0 mg/L. Under the indicated optimal conditions, the experimental findings verified that the removal efficiency was equal to Y = 98.92%, representing the highest observed value in this study. Under UVA light, after only 15 min of reaction, over 94% of dye was removed using both catalysts. The reuse experiments show that the activity of both nanohybrid material based on FePc-CNT slightly decreases over four consecutive runs. The quenching experiments show that RY84 was removed through radical pathways (O2•- and •OH) as well as non-radical pathways (1O2 and direct electron transfer). [ABSTRACT FROM AUTHOR]

Li2CO3 is the most tenacious parasitic solid-state product in lithium–air batteries (LABs). Developing suitable redox mediators (RMs) is an efficient way to address the Li2CO3 issue, but only a few RMs have been investigated to date, and their mechanism of action also remains elusive. Herein, we investigate the effects of the central metal ion in binuclear metal phthalocyanines on the catalysis of Li2CO3 decomposition, namely binuclear cobalt phthalocyanine (bi-CoPc) and binuclear cobalt manganese phthalocyanine (bi-CoMnPc). Density functional theory (DFT) calculations indicate that the key intermediate peroxydicarbonate (*C2O62−) is stabilized by bi-CoPc2+ and bi-CoMnPc3+, which is accountable for their excellent catalytic effects. With one central metal ion substituted by manganese for cobalt, the bi-CoMnPc's second active redox couple shifts from the second Co(II)/Co(III) couple in the central metal ion to the Pc(-2)/Pc(-1) couple in the phthalocyanine ring. In artificial dry air (N2-O2, 78:22, v/v), the LAB cell with bi-CoMnPc in electrolyte exhibited 261 cycles under a fixed capacity of 500 mAh g−1carbon and current density of 100 mA g−1carbon, significantly better than the RM-free cell (62 cycles) and the cell with bi-CoPc (193 cycles). [ABSTRACT FROM AUTHOR]

Metal Phthalocyanines (MPcs) undergo appreciable interaction mechanism with chemical analytes on account of their high sensitivity in terms of charge densities, optical and spectroscopic properties. In the present work, we aim to integrate the advantages of three MPcs with three different metal ions, similar functional group and a ligand attached to central metal ion to device chemresistor sensors. Four chemresistor devices were fabricated using permutation combinations of three MPcs; tetrasulfonic acid tetrasodium salt functionalized Nickel Phthalocyanine (NiPcS) and Copper Phtalocyanines (CuPcS) and Aluminium Phthalocyanine hydroxide (AlPcOH). The chemresistors were tested for surface-interface studies with an aromatic vapor benzene and strong oxidizing vapor bromine. For benzene, NiPcS–AlPcOH composite exhibited maximum sensitivity (≈ 2.73 ppm−1) and for bromine, CuPcS–AlPcOH composite shows highest sensitivity (≈ 72 ppm−1). [ABSTRACT FROM AUTHOR]

Chemical Communications is a journal published by The Royal Society of Chemistry, which is a leading chemistry community. The journal features articles on various topics in the chemical sciences. The contents list of the journal includes articles on subjects such as photoredox catalysis, supramolecular compounds, carbon nitride nanosheets, and more. The journal also highlights a cover image by Yun-Bao Jiang. The articles cover a range of research areas and provide valuable insights for those interested in chemistry. [Extracted from the article]

Here, photoelectrodes of photoelectrochemical (PEC) cells consisting of azide functionalized reduced graphene oxide (GO‐N3) and quaternary metal chalcogenide (CdZnNiSSe) composites sensitized with metal phthalocyanines (MPc, M: Co, Zn, Ti) are developed and then tested in hydrogen evolution reaction (HER). CdZnNiSSe/RGO‐N3 composite is deposited on an indium tin oxide (ITO) electrode through a facile electrodeposition technique and ITO/CdZnNiSSe/RGO‐N3 photoelectrode is constructed. Then, MPcs bearing terminal alkyne groups are connected to RGO‐N3 via the copper(I)‐catalyzed azide‐alkyne cycloaddition (click chemistry) technique to produce ITO/CdZnNiSSe/RGO‐N3‐MPc structures. Decoration of ITO/CdZnNiSSe/RGO‐N3 with MPcs is proposed to improve the charge transfer capability of the photoelectrode due to wide light absorption of MPcs from UV toward the IR region of the light spectrum. PECHER responses indicate that among the photoanodes bearing ZnPc, CoPc, and TiOPc, ITO/CdZnNiSSe/RGO‐N3‐ZnPc electrode exhibits the highest PECHER performance owing to the suitability of band structure of ZnPc. Sensitizing ITO/CdZnNiSSe/RGO‐N3 with ZnPc increases the photocurrent density from 5.0 to 7.3 mA cm−2 at 0.8 V vs. RHE and the applied bias photon to current efficiency (ABPE) enhances from 3.18 % to 3.87 %. This study provides a new approach for increasing the performance of photoanodes via sensitization with MPcs in photoelectrochemical hydrogen evolution processes for future applications. [ABSTRACT FROM AUTHOR]

1-[4-(4-Methoxyphenyl)azo]naphthol was synthesized using diazotization and azo coupling reactions. The compound was used as a nucleophile to prepare 3- and 4-[(4-methoxyphenylazo)-4-naphthoxy]phthalonitriles. The corresponding metal complexes of phthalocyanines were synthesized by the template condensation of the resulting substituted phthalonitriles with zinc and magnesium acetates. The influence of the substituent position on the protonation processes and spectroscopic characteristics of metal phthalocyanines was determined. The luminescence properties of the synthesized metal complexes and photosensitization of singlet oxygen were studied. [ABSTRACT FROM AUTHOR]

In this review, the state of research over the past fifteen years in the field of the applications of metal phthalocyanines and porphyrin derivatives as well as their hybrid materials with carbon nanotubes, metal oxides, and polymers in optical sensors based on the phenomenon of surface plasmon resonance (SPR) is analyzed. The first chapter of the review presents an analysis of works on the use of porphyrins and phthalocyanines in classical SPR sensors for the detection of gases and volatile organic vapors, as well as their improved modifications, such as total internal reflection ellipsometry (TIRE) and magneto-optical SPR (MOSPR) methods, while the second chapter is devoted to their application for the detection of various analytes in solutions. The third chapter of the review summarizes publications describing recent advances in the use of porous materials based on hybrids of carbon nanotubes and oxides with metal phthalocyanines. The fourth chapter describes two-dimensional metal-organic frameworks (MOFs) based on metal porphyrin derivatives as SPR sensitizers. [ABSTRACT FROM AUTHOR]

Catalytic synthesis of urea is a bright substitutable to Haber–Bosch progression and industrial urea synthesis. Electrochemical C–N coupling of carbon dioxide and nitrogen oxides under environmental conditions is a newly developed method, which also provides a novel opinion for solving nitrate contamination. Conjugated organic frameworks (COFs) have been used as prospective electrocatalysts for nitrogen reduction reactions and carbon dioxide reduction reactions (CO2RR) as a result of their regulate structure and multihole properties, resulting in efficient electron transfer. This paper reports the efficient synthesis of urea from carbon dioxide and nitrate over MoM1S-Pc-M2PPs COF (M as a transition metal) electrocatalyst. According to the calculation of DFT, it was found that it was difficult for carbon dioxide and nitrogen oxide to coadsorb on MoM1S-Pc to synthesize urea, so we chose to synthesize CO on the metal porphyrin (M2PPs) structural unit, and then overflow on the bimetallic phthalocyanine and nitrogen oxide to synthesize urea. The possibility of nitrate adsorption on different catalysts was verified by calculation. We screened the stability, nitrate adsorption strength, and catalytic activity of MoM1S-Pc candidates, and the results showed that the most promising candidate catalyst was MoFeS-Pc. At the same time, the CO2RR M2PPs substrate was also screened, and the VPPs structure was selected as the best. In the study of coupling between different nitrogen-containing intermediates and *CO, the C–N coupling mechanism shows that *NOH and *CO are two possible C–N coupling nitrogen intermediates, which are shown to be thermodynamically spontaneous and have an inferior activation barrier. This study not only provisions novel perceptions into urea synthesis by coupling nitrogen oxides with carbon dioxide under environmental conditions, but also paves the way for boosting the sustainable production of carbon and nitrogen-coupled products. [ABSTRACT FROM AUTHOR]

Bi- and trimetallic catalysts based on multi-walled carbon nanotubes (MWCNT) and metal (Me) phthalocyanines (Pc) (MePc) (MWCNT–CoPc–NiPc, MWCNT–CuPc–NiPc, MWCNT–CoPc–CuPc, and MWCNT–CoPc–CuPc–Pd) for electrochemical oxygen reduction reaction (ORR) were synthesized by high-temperature synthesis at 1000°C in an inert atmosphere. The obtained materials were characterized by scanning electron microscopy (SEM), low-temperature nitrogen absorption–desorption, and Raman spectroscopy. The change in textural characteristics and morphology of electrocatalysts during high-temperature synthesis was studied. It was shown that the nature of the metal significantly changes the physicochemical characteristics of electrocatalysts based on carbon nanotubes. The electrochemical experiment was carried out in the linear voltammetry algorithm using a three-electrode chamber with a rotating disk electrode. The main characteristics of the process of electroreduction of oxygen from an alkaline electrolyte—limiting diffusion current, potential half-waves, and initial reaction potential—were determined. MWCNT–CoPc–CuPc–Pd catalyst was found to exhibit the highest activity in the reaction of electrochemical oxygen reduction in an alkaline liquid, reaching high efficiency and corrosiveness as with platinum catalysts, with a decrease in activity after 1000 cycles of less than 7%. [ABSTRACT FROM AUTHOR]

Highlights Compared with the traditional single-atom catalysts (SACs), the Mg SACs with axial displacement is accurately fabricated on the functional carbon nanotubes. The electronic spin polarization modulates the spin density of MgPc, facilitating the LiPSs conversion kinetics in Li-S batteries. The MgPc@FCNT achieves ultra-low capacity decay rate under the high sulfur loading.

The nonlinear optical limiting (OL) property of tin phthalocyanine porous organic frameworks (Sn-Pc-POFs) dispersion in the nanosecond regime was studied, which showed excellent dispersibility and stability as well as a low OL threshold. To clarify the nonlinear optical response mechanisms in the material, the energy level structure of Sn-Pc-POFs was simulated using the density functional theory calculation, and the photoinduced carrier dynamics was studied using femtosecond time-resolved transient absorption spectroscopy. The results indicated that the large absorption cross section and long lifetime of the excited state were responsible for the excellent OL property of the material. [ABSTRACT FROM AUTHOR]

Interfaces formed between monolayer transition metal dichalcogenides and (metallo)phthalocyanine molecules are promising in energy applications and provide a platform for studying mixed-dimensional molecule-semiconductor heterostructures in general. An accurate characterization of the frontier energy level alignment at these interfaces is key in the fundamental understanding of the charge transfer dynamics between the two photon absorbers. Here, we employ the first-principles substrate screening GW approach to quantitatively characterize the quasiparticle electronic structure of a series of interfaces: metal-free phthalocyanine (H2Pc) adsorbed on monolayer MX2 (M = Mo, W; X = S, Se) and zinc phthalocyanine (ZnPc) adsorbed on MoX2 (X = S, Se). Furthermore, we reveal the dielectric screening effect of the commonly used α-quartz (SiO2) substrate on the H2Pc:MoS2 interface using the dielectric embedding GW approach. Our calculations furnish a systematic set of GW results for these interfaces, providing the structure–property relationship across a series of similar systems and benchmarks for future experimental and theoretical studies. [ABSTRACT FROM AUTHOR]

Triplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair 1(T1T1) is prone to triplet‐triplet annihilation due to its spatial confinement. In the solid state, entropically driven triplet diffusion assists in the spatial separation of triplets, resulting in higher yields of free triplets. Control over electronic coupling in the solid state is, however, challenging given its sensitivity to molecular packing. We have thus developed a hexameric system (HexPnc) to enable solid‐state‐like triplet diffusion at the molecular scale. This system is realized by covalently tethering three pentacene dimers to a central subphthalocyanine scaffold. Transient absorption spectroscopy, complemented by theoretical structural optimizations and steady‐state spectroscopy, reveals that triplet diffusion is indeed facilitated due to intramolecular cluster formation. The yield of free triplets in HexPnc is increased by a factor of up to 14 compared to the corresponding dimeric reference (DiPnc). Thus, HexPnc establishes crucial design aspects for achieving efficient triplet dissociation in strongly coupled systems by providing avenues for diffusive separation of 1(T1T1), while, concomitantly, retaining strong interchromophore coupling which preserves rapid formation of 1(T1T1). [ABSTRACT FROM AUTHOR]

Metallo-phthalocyanines (MPcs) are macrocycles of synthetic origin that are highly conjugated and planar, with high absorption in the ultraviolet–visible region. When combined with nanomaterials such as graphene, they offer the possibility of developing systems for nanobiotechnology. In this work, the modifications arising from the incorporation of the transition metals Fe, Mn, and Cu into the Pc structure, forming MPcs, are evaluated using first principles calculations. These metals are observed to interact strongly with Pc to form stable complexes. The interaction of graphene with MPc was then studied to understand the energetic, magnetic, and structural properties of these structures, which may help in the use of these nanomaterials in future biomedical applications. From the results, we can observe that depending on the metal introduced into MPc, different values ​​are found for the charge transfer and spin polarisation between the systems; however, each complex shows weak interaction between graphene and MPc, suggesting physical adsorption. [ABSTRACT FROM AUTHOR]

In this investigation, new 4-Tetra-4-Tolyl-Sulfonyl:Iron-Phthalocyanine (4T4TS-FePc) thin films' physical properties were examined using a variety of experimental conditions. The structural, morphological and optical properties of 4T4TS-FePc thin films were studied using different methods and also show that over appropriate heat treatment, it is possible to obtain 4T4TS-FePc films with a morphology tailored particularly to the desired needs including photocatalysis. According to the X-ray results, the film transfigures into a monoclinic ( β -phase) structure at an annealing temperature of 200 °C, and the reported diffraction peaks are subsequently lost at this phase shift. The material stands out from other compounds due to its qualities for thin-film mechanical and chemical stability. Subsequently, the methylene blue degrades quickly (to reaching 41.66%) when exposed directly to resilient visible radiation (λ ≥ 400 nm) for more than six hours, which is consistent with the rest of the features of these hybrid compounds indicating their significant potential as a photocatalyst. As a result, its potential for applications is evident for the treatment of wastewater. [ABSTRACT FROM AUTHOR]

[Display omitted] CO 2 electrochemical reduction is a sustainable approach to achieve chemical fixation of CO 2 and storage of renewable energy. However, the catalyst which has the ability of mediating CO 2 to a single product with a relatively high current density is highly demand. Herein, we reported a metallic nitrogen-carbon catalyst based on two kinds of metal phthalocyanines by a facile synthesis method. The synergistic effect of Cu and Ni and the active sites of nickel oxide/copper nanocluster endow the catalyst excellent performance towards CO 2 -into-CO electroreduction. Typically, the Cu-Ni bimetallic catalyst achieves high selectivity (85.2 %) at positive potential (−0.72 V RHE), with the stability of current density and product selectivity beyond 72 h. The volume ratio of CO/H 2 can be effectively tuned (from 2:1, 1:1 to 1:2) by controlling the electrolysis potential, which is promising for synthesis gas in the Fischer-Tropsch reactions and methanol synthesis. Furthermore, the advantages are further amplified by applying it to zero-gap membrane flow reactor, which can enhance the selectivity over 90 % at a broad potential range (−2.5 ∼ −2.7 V) and achieve an current density of 9-fold of H-type cell. Our work proves a way for optimizing the CO 2 electrocatalyst and electrolyzers. [ABSTRACT FROM AUTHOR]

In this work we studied the semiconductor behavior of titanyl phthalocyanine (TiOPc) and vanadyl phthalocyanine (VOPc), doped with anthraflavic acid and deposited on Tetrapak/graphite as flexible electrodes. The molecular structure was approached using the density functional theory and astonishingly, it was found that the structure and electronic behavior can change depending on the metal in the phthalocyanine. Experimentally, the Root Mean Square was found to be 124 and 151 nm for the VOPc-Anthraflavine and TiOPc-Anthraflavine films, respectively, and the maximum stress was 8.58 MPa for the film with VOPc. The TiOPc-Anthraflavine film presents the smallest fundamental gap of 1.81 eV and 1.98 eV for indirect and direct transitions, respectively. Finally, the solid-state devices were fabricated, and the electrical properties were examined. The tests showed that the current–voltage curves of the devices on Tetrapak and VOPc-Anthraflavine on a rigid substrate exhibit the same current saturation behavior at 10 mA, which is achieved for different voltage values. Since the current–voltage curves of the TiOPc-Anthraflavine on a rigid substrate presents a defined diode model behavior, it was approximated by nonlinear least squares, and it has been determined that the threshold voltage of the sample for the different lighting conditions is between 0.6 and 0.8 volts. [ABSTRACT FROM AUTHOR]

A sulfonyl-chloride-modified lignin-based porous carbon-supported metal phthalocyanine catalyst was prepared and used to replace the traditional Fenton's reagent for lignin degradation. The catalyst underwent a detailed characterization analysis in terms of functional group distributions, surface area, morphological structure, via FT-IR, XPS, BET, and SEM. The catalyst possessed a specific surface area of 638.98 m2/g and a pore volume of 0.291 cm3/g. The prepared catalyst was studied for its ability of oxidative degradation of lignin under different reaction conditions. By optimizing the reaction conditions, a maximum liquid product yield of 38.94% was obtained at 135 °C with 3.5 wt% of catalyst and 15 × 10−2 mol/L H2O2; at the same time, a maximum phenols selectivity of 32.58% was achieved. The compositions and properties of liquid products obtained from lignin degradation using different catalyst concentrations were studied comparatively via GC-MS, FT-IR, 1H-NMR, and EA. Furthermore, the structure changes of solid residues are also discussed. [ABSTRACT FROM AUTHOR]

A detailed inverse photoemission study unveils the unoccupied electronic structure induced by the adsorption of CuPc and CoPc phthalocyanines on Au(110) reconstructed channels. The different behavior in the two systems is related to the different intermixing of orbitals with the underlying gold states. Broadening of the density of states at the Fermi level is detected after CoPc adsorption, absent in the case CuPc. A detailed comparison with the element-selective X-ray absorption spectroscopy enlightens and complements the IPES results and confirms a surface-driven intermixing of the CoPc orbitals involved in the interaction, with the out-of-plane Co 3dz2 orbital strongly hybridized with the gold electronic states. Moreover, the contribution of the 3d empty states to the IPES data is reported for FePc, CoPc, and CuPc thin films. [ABSTRACT FROM AUTHOR]

This article provides a polyphenol-mediated modulation (PMM) strategy for the controllable assembly of hollow hybrid nanomaterials (HZIF-8/PcFe and HZIF-8@PcFe) with different TA (tannic acid) coating thicknesses to detect dopamine, which exhibit excellent linearity range (0.3–200 μmol/L) with a detection limit as low as 0.1 μmol/L (S/N = 3). [Display omitted] Multiple microenvironmental modulation of zeolite imidazole framework-8 (ZIF-8) is expected to solve the long-term intractable problem of low sensitivity in electrochemical sensing. Herein, the metal phthalocyanines with different central ions (PcM, M = Fe, Co, Ni and Cu) were introduced into ZIF-8 by in-situ synthesis method. Then, the hollow composite nanomaterials, HZIF-8/PcFe and HZIF-8@PcFe (HZIF-8, i.e., hollow ZIF-8) with different TA (tannic acid) coating thicknesses (∼11 nm and ∼33 nm) were successfully fabricated by carefully designed polyphenol-mediated modulation (PMM) strategy. Next, the HZIF-8@PcFe electrochemical sensor was constructed for selective and sensitive analysis by selecting dopamine (DA) as the analyte. The TA coating (superhydrophilic state), PcFe (redox properties) and hollow MOF cavity (faster mass transfer) was used as the triple microenvironment modulation of ZIF-8 to enhance the electrocatalytic performance. Under the optimum conditions (pH = 8.0), the linear correlations of 0.3 to 200 μmol/L was obtained for the peak current response, with a detection limit of 0.1 μmol/L (S/N = 3, i.e., Signal/Noise = 3). Meanwhile, the HZIF-8@PcFe electrochemical sensor exhibited excellent interference selectivity, reproducibility and stability, which enabled it to detect low abundance DA in real samples. And the F-test (homogeneity test of variance) and t -test (student's t test) statistical analyses were employed to enhance the accuracy of the actual samples' detection. This work will enlighten researchers working in the field of porous framework composites and open up new paths for the development of hollow MOFs hybrid materials in electrochemical sensing. [ABSTRACT FROM AUTHOR]

Phthalocyanines are artificial macrocycles that can harbour a central metal atom with four symmetric coordinations. Similar to metal-porphyrins, metal-phthalocyanines (M-PCs) may bind small molecules, especially diatomic gases such as NO and O2. Furthermore, various chemical chains can be grafted at the periphery of the M-PC macrocycle, which can change its properties, including the interaction with diatomic gases. In this study, we synthesized Zn-PCs with two different substituents and investigated their effects on the interaction and dynamics of nitric oxide (NO). Time-resolved absorption spectroscopy from picosecond to millisecond revealed that NO dynamics dramatically depends on the nature of the groups grafted to the Zn-PC macrocycle. These experimental results were rationalized by DFT calculations, which demonstrate that electrostatic interactions between NO and the quinoleinoxy substituent modify the potential energy surface and decrease the energy barrier for NO recombination, thus controlling its affinity. [ABSTRACT FROM AUTHOR]

Transition metal‐catalyzed, non‐enzymatic nitrene transfer (NT) reactions to selectively transform C−H and C=C bonds to new C−N bonds are a powerful strategy to streamline the preparation of valuable amine building blocks. However, many catalysts for these reactions use environmentally unfriendly solvents that include dichloromethane, chloroform, 1,2‐dichloroethane and benzene. We developed a high‐throughput experimentation (HTE) protocol for heterogeneous NT reaction mixtures to enable rapid screening of a broad range of solvents for this chemistry. Coupled with the American Chemical Society Pharmaceutical Roundtable (ACSPR) solvent tool, we identified several attractive replacements for chlorinated solvents. Selected catalysts for NT were compared and contrasted using our HTE protocol, including silver supported by N‐dentate ligands, dinuclear Rh complexes and Fe/Mn phthalocyanine catalysts. [ABSTRACT FROM AUTHOR]

Ammonia (NH3) is regarded as a renewable energy source as well as an important molecule for agricultural applications. The energy‐intensive Haber‐Bosch method produces large amounts of CO2 gas during ammonia production. As an alternative, there has recently been much interest in the electrocatalytic production of NH3 via the electrochemical nitrogen reduction reaction (ENRR) process utilizing renewable energy under ambient condition. Herein, we report a conducting carbon–supported manganese phthalocyanine electrocatalyst as an efficient electrocatalyst for ENRR applications. The MnPc electrocatalyst exhibited the activity with an ammonia production rate of 61.8 μg h−1mg−1cat with Faradaic efficiency (FE) of 31.3% @–0.4 V vs. RHE, respectively, under ambient condition in 0.1 M HCl solution whereas MnPc/C electrocatalyst exhibited an enhanced the productivity with an ammonia yield rate of 127.7 μg h−1mg−1cat with FE of 35.3% @–0.4 V vs. RHE, respectively. The reliability of N origin in ammonia formation is demonstrated by 1H‐NMR experiments and multiple control analysis. These results open the way for the further study of carbon‐supported transition‐metal phthalocyanine compounds for electrochemical nitrogen fixation to NH3. [ABSTRACT FROM AUTHOR]

Iron ions in a square‐planar coordination can bind molecules at the vacant axial positions and are able to transform them in stoichiometric and catalytic reactions. Nature takes advantage of these properties by incorporating iron into porphyrin systems, which play a key role not only in the binding and transport of oxygen, but also in catalytic oxidation and reduction reactions involving cytochrome P450. Although these systems have been studied extensively, there are still unresolved questions regarding the interplay between the iron ions and the surrounding ligands. Phthalocyanines (Pc) create a similar environment for metal atoms and FePc is known for a long time. However, without axial ligands FePc aggregates leading to solids of low solubility. In this work we used a known six‐coordinate iron phthalocyanine derivative with bulky substituents and removed the stabilizing axial ligands. The resulting paramagnetic, four‐coordinate compound does not aggregate and dissolves well so that NMR spectroscopy can be employed for studying the molecular structure and the reactivity. Solvent molecules bind weakly to the iron centers and oxygen is reduced in the presence of H‐atom donors. The stoichiometric and catalytic reactivity with oxygen was studied in more detail. [ABSTRACT FROM AUTHOR]

This study examined NH 3 decomposition over the metal clusters on titanium phthalocyanines (M 6 @TiPc; M 6 = Fe 6 , Co 6 , Ni 6 , Co 5 Ni, and Ni 5 Co). The M 6 metal clusters could stably adsorb on TiPc. The Brønsted–Evans–Polanyi relations were found in the dehydrogenation step and the step for associative desorption of nitrogen. The latter was the rate-determining step for decomposing NH 3. Moreover, the positive electric field promoted the dehydrogenation step by weakening the adsorption strength of NH 3. In contrast, the negative electric field improved the step for associative desorption of nitrogen by reducing the adsorption strength of nitrogen. Overall, this study offers insight into the design of the high-performance M 6 @TiPc-based catalyst for decomposing NH 3. • The catalytic performance of the metal clusters (M 6) on TiPc for NH 3 decomposition was assessed. • Brønsted–Evans–Polanyi relations were found in the dehydrogenation step and the step for associative desorption of nitrogen. • The associative nitrogen desorption was found as the rate-determining step for the decomposition of ammonia. • The positive electric field promoted the dehydrogenation step by weakening the adsorption strength of NH 3. • This study offers insight into the development of the M 6 @TiPc-based catalyst for decomposing ammonia. [ABSTRACT FROM AUTHOR]

This paper focuses on incorporation of graphene oxide (GO) to metal‐free phthalocyanine (MPc) through only hydrogen bonding and π‐π stacking. Briefly, Pc‐GO composites at various concentrations were prepared by self‐assembly method. The processing time was kept below 10 min to avoid covalent attachment and we aimed at answering the research question of what will happen if the conjugation is realized only through hydrogen bonding under extremely limited processing times. The as‐prepared MPc‐GO composites were characterized by Fourier transform infrared (FT‐IR), UV‐Vis, scanning electron microscope (SEM), and fluorescence analysis. We report that the interaction between MPc and GO could immediately be initiated upon mixing of corresponding solutions. Also, complete conjugation by hydrogen bonding and π‐π stacking could be reached even only in 5 min of sonication time. In addition, it was also determined that the prepared MPc‐GO composites are stable at room conditions and during dilution. Finally, the optoelectronic properties of MPc and MPc‐GO composites were also investigated experimentally and theoretically. Both experimental and theoretical results suggest that MPc‐GO composites exhibit improved optoelectronic properties as compared to MPc, even though the conjugation of GO to MPc was only via hydrogen bonding without covalent attachment. [ABSTRACT FROM AUTHOR]

Abstract Here, photoelectrodes of photoelectrochemical (PEC) cells consisting of azide functionalized reduced graphene oxide (GO‐N3) and quaternary metal chalcogenide (CdZnNiSSe) composites sensitized with metal phthalocyanines (MPc, M: Co, Zn, Ti) are developed and then tested in hydrogen evolution reaction (HER). CdZnNiSSe/RGO‐N3 composite is deposited on an indium tin oxide (ITO) electrode through a facile electrodeposition technique and ITO/CdZnNiSSe/RGO‐N3 photoelectrode is constructed. Then, MPcs bearing terminal alkyne groups are connected to RGO‐N3 via the copper(I)‐catalyzed azide‐alkyne cycloaddition (click chemistry) technique to produce ITO/CdZnNiSSe/RGO‐N3‐MPc structures. Decoration of ITO/CdZnNiSSe/RGO‐N3 with MPcs is proposed to improve the charge transfer capability of the photoelectrode due to wide light absorption of MPcs from UV toward the IR region of the light spectrum. PECHER responses indicate that among the photoanodes bearing ZnPc, CoPc, and TiOPc, ITO/CdZnNiSSe/RGO‐N3‐ZnPc electrode exhibits the highest PECHER performance owing to the suitability of band structure of ZnPc. Sensitizing ITO/CdZnNiSSe/RGO‐N3 with ZnPc increases the photocurrent density from 5.0 to 7.3 mA cm−2 at 0.8 V vs. RHE and the applied bias photon to current efficiency (ABPE) enhances from 3.18 % to 3.87 %. This study provides a new approach for increasing the performance of photoanodes via sensitization with MPcs in photoelectrochemical hydrogen evolution processes for future applications.

Iron phthalocyanines play crucial fundamental and applied roles ranging from bulk colorants to components of advanced materials. In this Frontier article, we discuss four aspects concerning the influence of the axial ligands on spectroscopic and redox properties of iron(II) phthalocyanines: (i) iron versus macrocycle oxidation cite as a function of Lever's EL parameter; (ii) energy of the metal-to-ligand charge-transfer transitions as a function of Lever's EL parameter; (iii) iron versus macrocycle reduction in iron(II) phthalocyanines; (iv) Mössbauer quadrupole splitting as a function of axial ligand binding through the prism of dz2 orbital population. [ABSTRACT FROM AUTHOR]

Metal phthalocyanines, which are examples of one-dimensional semiconductors, are widely used as active layers of chemiresistive sensors for detecting various gases, in particular ammonia. Despite the high interest in such sensors, there have been few systematic studies on the effect of the type of substituent and structural features of films on their chemiresistive response to gases. In this work, films of zinc phthalocyanine (ZnPc-1, 2, 3 and 4) bearing alkylthio (–S(CH2)5CH3) and polyoxo (–O(CH2CH2O)3CH3 and –S(CH2CH2O)3CH3) substituents, which exhibit liquid crystalline properties and, as a consequence, are capable of forming ordered films, were tested as active layers of chemiresistive sensors for the detection of low concentrations of ammonia (0.1–50 ppm). The effect of the type of substituent on the films' alignment and sensor response to ammonia was studied for the first time. It was shown that the films of all investigated zinc phthalocyanines demonstrated a reversible chemiresistive sensor response to gaseous ammonia. The sensor response of the as-deposited films of ZnPc-1 and ZnPc-2 with polyoxo-substituents, which are liquid crystalline at room temperature, was noticeably higher than that of ZnPc-3 and ZnPc-4, which form polycrystalline disordered films. The limit of ammonia detection was 17 ppb for ZnPc-1 and ZnPc-2 films. Heat treatment of ZnPc-1 and ZnPc-2 films did not cause any changes in their structure and sensor properties, while ZnPc-3 and ZnPc-4 films became more ordered after heating, and their sensor response increased several times. This led to a reduction in the detection limit of ammonia to 10 ppb in the case of the ZnPc-3 film. All investigated films have high selectivity to ammonia in the presence of carbon dioxide and vapors of some volatile organic compounds. [ABSTRACT FROM AUTHOR]

An analysis of the nanostructure morphology of ionic carboxyl-containing phthalocyanine and tetrasodium salt of Cu(II)-phthalocyanine-tetrasulphonic acid in the structure of latex polymers is carried out using optical and quasi-optical methods: optical microscopy, atomic-force microscopy (AFM), and fluorescence and Raman spectroscopy. The variety of shapes and sizes of the phthalocyanine nanostructures localized in the interparticle space of the latex polymers is analyzed, which determines the difference in their photochemical properties. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]