Macroheterocycles

Content. Second cover page

2025-07-07T23:05:32+03:00

Boron(III) Subphthalocyanines Axially Modified with Unsaturated and Aromatic Carboxylic Acids: Synthetic Peculiarities and Photochemical Properties

2025-07-07T23:05:32+03:00

In this work, the axial modification of boron(III) subphthalocyanine (sPc) with several unsaturated and aromatic carboxylic acids was performed for the first time. Acrylic acid (AA), maleic acid (MA), fumaric acid (FA), and terephthalic acid (TA) were used as precursors. During the substitution reaction of axial bromine in the initial subphthalocyanine with acrylate, the formation of acrylic acid esterification products (sPcAA1-3) was observed. A range of photophysical parameters (quantum yield and fluorescence lifetime) was obtained for all compounds, and the generation of singlet oxygen in DMSO and ethanol was studied. The series of subphthalocyanines examined exhibited high quantum yields of singlet oxygen generation and can be considered as a new type of monomeric photosensitizers with potential for immobilization on the surface of various matrices due to the presence of anchor carboxylic groups. This development could lead to hybrid photoactive materials for oxidative applications in photocatalysis and photodynamic therapy (PDT).

Synthesis, Optical Properties and Thermal Stability of Octa(p-chlorophenoxy) Substituted Phthalocyanine Complexes of Magnesium(II) and Zinc(II)

2025-07-07T23:05:37+03:00

The present study is a continuation of the work on the synthesis and study of the properties of octa(p-chlorophenoxy)-substituted phthalocyanines. In the previous study, the optical characteristics of the lutetium complex were described. The present work is devoted to zinc and magnesium complexes. Comparative studies of absorption and luminescence spectra were carried out. The thermal stability of the target compounds up to 800^оС was studied by thermogravimetry with synchronous mass spectrometric analysis.

Experimental and Theoretical Study of Cobalt Hemiporphyrazine Behavior in the Gas Phase by Mass Spectrometry

2025-07-08T16:35:19+03:00

The vapor composition and the enthalpy of sublimation of the cobalt(II) hemiporphyrazine (CoHp) complex were determined by the Knudsen effusion method using mass spectrometric MI-1201 modified for high temperature investigations. Electron ionization mass spectra were also simulated using the QCxMS program implemented in the xTB software package. The enthalpy of sublimation for CoHp determined using the Clausius-Clapeyron equation is 212(5) kJ/mol in the temperature range of 481–544 K. The energy of intermolecular interaction was estimated using the criterion proposed by Espinosa for both H₂Hp and CoHp within the framework of QTAIM theory. The difference between the energies of intermolecular interactions of H₂Hp and CoHp was about 20 kJ/mol. In the case of experimental values of the enthalpies of sublimation for H₂Hp and CoHp, the difference was also 20 kJ/mol.

Cu(II) porphyrin-Mediated Reed-Straw-Carbon-Based Cu-N-C Catalysts for Efficient Electrocatalytic Nitrate Reductions

2025-07-07T23:05:40+03:00

Herein, the Cu^IIporphyrin-mediated reed-straw-carbon-based Cu-N-C catalyst was prepared through high-temperature thermal treatment, and the structures were characterized by SEM, XRD, Raman, FT-IR and XPS. During the electrocatalytic experiments, the Cu-N-C catalyst exhibits excellent nitrate reduction performance (56.33%) and high energy utilization efficiency (63.16%) at E = -1.3V. Also, the electrocatalytic stability and ion influence in the simulated waste water were also investigated. These results provide an opportunity to further explore the efficient electrochemical removal of nitride from M-N-C catalysts.

Synthesis and Evaluation of the Cytotoxicity of Zinc Porphyrinates Derived from Protoporphyrin IX Derivatives

2025-07-07T23:05:40+03:00

New zinc complexes of protoporphyrin IX derivatives, specifically the dimethyl esters of deuteroporphyrin IX and mesoporphyrin (1 and 2), as well as their amide derivatives containing an ethanolamine fragment (3 and 4), were synthesized. The compounds obtained, with the exception of the Zn-1 complex, exhibited low solubility, which precluded the evaluation of their dark cytotoxicity at concentrations exceeding 25 μM. The flow cytometry analysis demonstrated that ligands 1, 3, and 4, along with the corresponding Zn-1 to Zn-4 complexes, were able to penetrate HeLa cells. The photoinduced cytotoxicity of the compounds studied was observed at concentrations lower than 1 μM. Fluorescence microscopy revealed that Zn-1 molecules are localized both in mitochondria and the Golgi apparatus. Photoinduced exposure of Zn-1 to HeLa cells resulted in an increase in reactive oxygen species levels and a decrease in mitochondrial membrane potential. Together with phosphatidylserine externalization, these results suggest a possible induction of regulated cell death after photoinduced exposure to Zn-1.