This work is devoted to the synthesis and study of the molecular structure of the tetra-3-(4- cyclohexylphenoxy)phthalocyanine aluminum chloride complex. The synthesis of tetra-3-(4-cyclohexylphenoxy)phthalocyanine aluminum chloride was carried out by the "nitrile" method. The complex was purified by M60 silica gel column chromatography, eluting with the chromophore. IR-spectroscopy and mass-spectrometry (MALDI-TOF) were used for the identification of the obtained compound. The electronic absorption spectrum was obtained in tetrahydrofurane and interpreted by quantum-chemical calculations in TDDFT approximation. The conformational search was performed utilizing the CREST program and GFN2-xTB approximation, followed by DFT calculations of the "single-point" energies of the found conformations. For each configuration, "single-point" energy calculations were carried out in the B3LYP-D3/dgdzvp approximation and the most energetically favorable structure was identified. It has been established that the most energetically favorable structure of the tetra-3-(4-cyclohexylphenoxy)phthalocyanine aluminum chloride molecule is characterized by a helical mutual arrangement of bulky substituents on the same side of the macrocyclic plane. The interpretation of the electronic absorption spectrum was made on the basis of TDDFT calculations in the B3LYP-D3/def2-TZVP and CAM-B3LYP/def2-TZVP approximations with and without solvent (tetrahydrofuran, THF) within the C-PCM continuum solvation model. For both approximations, taking into account the solvent leads to a shift of the longwavelength absorption maximum by 25-33 nm towards the experimental value (704 nm). The best agreement with experiment is achieved with the [PCM] CAM-B3LYP/def2-TZVP method. The simulated electronic spectrum is compared with the previously obtained spectra for complexes of Al(Cl) with tetrabenzoporphyrin (ClAlTBP) and tetrapyrazinoporphyrazine (ClAlTPyzPA).

The equilibrium structure of free 4-(4-hydroxyphenylazo)phthalonitrile (p-HPhAPN, C14N4H8O) molecules was investigated for the first time by combined gas-phase electron diffraction and mass spectrometry (GED/MS) experiment, as well as through quantum chemical (QC) calculations. It was determined that p-HPhAPN in the vapor is represented by planar azo forms. & Scy;is-trans isomerism, azo-hydrazone tautomerism and rotations of different moieties in p-HPhAPN were studied in B3LYP-D3/pcseg-2 and DLPNO-CCSD(T0) levels of theory. Electron impact mass spectra of p-HPhAPN are typical for azobenzenes and are interpreted using the results of QCxMS calculations at the GFN2-xTB level of theory. Due to the exciting possibility of p-HPhAPN in the preparation of phthalocyanines with macrocyclic and azo chromophores, the structures of corresponding isomers of zinc phthalocyanines were investigated.

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.

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

The electrochemical and electrocatalytic behavior of gold electrodes modified with tetra-4-sulfophthalocyaninates of nickel(II) (NiPc) and copper(II) (CuPc) is studied in aqueous alkaline solutions using cyclic voltammetry. The electrocatalytic activity of phthalocyaninates of these metals in the oxidation of hydroxide ions to form molecular oxygen is assessed and compared with the literature data.

The work describes the optimization of the procedure for the synthesis of 4-bromo-2-methoxyphenyldiazenylphenol, which is used as a nucleophile in the presence of 3- and 4-nitrophthalonitriles. The resulting 3-(4-bromo-2-((4-methoxyphenyl)diazenyl)phenoxy)- and 4-(4-bromo-2-((4methoxyphenyl)diazenyl)phenoxy)phthalonitriles were used for template condensation with magnesium or zinc acetate. Methods for isolating and purifying the synthesized compounds are described. The structure and composition were confirmed using IR, 1H NMR and electron spectroscopy. Peripheral functionalization of macrocycle by a conjugate azochromophore fragment gives molecules phthalocyanine with special optical properties. This class of phthalocyanines containing an additional chromophore system in their composition is attractive for potential use not only as pigments and dyes traditional for phthalocyanine compounds, but also as chemical sensors, dyesensitized solar cells and photosensitizers for PDT. The resulting nitriles and phthalocyanine complexes dissolve in chloroforms, toluene, THF, and DMF. The influence of the substituent location on the spectral properties of the obtained metal complexes (Zn, Mg) in organic solvents has been studied. For non -peripherally substituted metal phthalocyanines, acid -base properties are studied. To observe and study the acid -base effect, spectrophotometric titration of the trifluoroacetic acid complex in toluene is used. It is shown that the magnesium complex is more basic than the zinc complex. In this work, the luminescent properties are also studied and the quantum yields of singlet oxygen formation for synthesized complexes in THF are determined. The influence of the substituent location on the quantum yield of fluorescence, as well as on the generation of singlet oxygen, is noted in the work.

The review presents a generalization of research on the chemistry of solutions and mate-rials based on linear and cyclic polypyrrole compounds carried out at the Department of Inorgan-ic Chemistry of the Ivanovo State University of Chemistry and Technology. The review focuses on key areas related to synthetic approaches to the preparation of boron complexes with pyrrole de-rivatives, as well as complexes of a wide range of metals of the periodic system with substituted derivatives of the phthalocyanine ligand. Spectroscopic, luminescent, acid-base properties of syn-thesized compounds and their practical application in sensor systems are considered separately. In addition, the possibilities of obtaining hybrid and functional materials, including derivatives of borondipyrrins and tetrapyrrole macroheterocyclic compounds, which have increased catalytic and biological activity in liquid-phase processes are shown.

The electrochemical behavior of tetra-4-[4-(2,4,5-trichlorophenoxy)]phthalocyaninates of cobalt(II) (CoPc) and copper(II) (CuPc) in N,N-dimethylformamide with 0.1 M nBu4NBF4 as a supporting electrolyte is studied by cyclic voltammetry. It is shown experimentally that both metal complexes are capable of irreversible reduction. In this case, the reverse CV-scan for CoPc demonstrates an oxidation peak which is absent in the anodic scan and corresponds to the cathodic reaction product. The metal complexes themselves are not oxidized under these conditions.

4-[4-Bromo-2-(2-phenyldiazenyl)phenoxy]phthalonitrile was obtained by the reaction of 4-nitrophthalonitrile and sodium 4-bromo-2-(2-phenyldiazenyl)phenolate. Magnesium and zinc phthalocyaninates were synthesized by the template condensation of the corresponding metals with phthalonitrile. The luminescence properties and photosensitization of singlet oxygen for the synthesized complexes were studied.

The synthesis of peripherally and non-peripherally substituted complexes of Zn(II), Mg(II), and Er(III) phthalocyanines based on 3(4)-(4-methylphenyldiazenylphenoxy)phthalonitrile was proposed. The effects of the complex-forming metal and the location of the substituent on the spectral properties of the synthesized compounds were shown. The acid-base properties of non-peripherally substituted metal phthalocyanines were studied. The fluorescence quantum yields and lifetimes of fluorescence for the synthesized metal complexes were determined.

The syntheses and crystal structures are reported of 4-phenoxy-substituted phthalonitriles with methoxy groups in the ortho- and meta-positions of the terminal benzene rings, respectively, namely, 4-(2-methoxyphenoxy)phthalonitrile and 4-(3-methoxyphenoxy)phthalonitrile, both C15H10N2O2. The https:// journals.iucr.org/e/issues/2023/03/00/molecular structure was determined using the single-crystal X-ray diffraction method. It is shown that short contacts play a more decisive role in the molecular packing compared to van der Waals interactions.

The authors obtain complexes CuPc(4-S-C 6 H 4 -COOH) 4 and CuPc(4-O-C 6 H 4 -COOH) 4 that are insoluble in water. The standard enthalpies of formation of these compounds are calculated using additive groups based on group systematics with Benson-type classification of fragments, allowing for the influence of the atoms’ primary environment. Thermal effects of the dissolution of crystalline phthalocyanines in aqueous solutions of various KOH concentrations at a temperature of 298.15 K were determined via direct calorimetry. Thermal effects of the stepwise dissociation of CuPc(4-S-C 6 H 4 -COOH) 4 , CuPc(4-O-C 6 H 4 -COOH) 4 are calculated using the HEAT computer program. Standard enthalpies of formation are calculated for products of the dissociation of CuPc(4-S-C 6 H 4 -COOH) 4 and CuPc(4-O-C 6 H 4 -COOH) 4 in an aqueous solution.

Present work reveals the study of catalytic properties of copper and cobalt complexes with phthalocyanine ligands with o-carboxyphenoxy/carboxyphenylsulfanyl/carboxyphenylamino -substituents in the peripheral positions of the macroring.For compounds, the aggregative behavior in aqueous and aqueous -alkaline media was studied.On the example of the reaction of catalytic oxidation of sodium N,N -diethyldithiocarbamate, the rate constants of the fo rmation of the corresponding disulfide were determined.The influence of the nature of the spacer fragment of the p eripheral substituent on the activity of the complexes as catalysts for liquid -phase oxidation was revealed.

During the synthesis of double-decker f-metal phthalocyanine complexes Ln(Pc)2 free phthalocyanine ligands can be also formed, however, routine column chromatography is not effective for their separation. The preliminary reduction of the complexes with hydrazine hydrate affords the low mobile forms, which can be re-oxidized in the chromatography columns after the free ligand is eluted.

In this paper, the method of cyclic voltammetry was used for the first time to study the electrochemical behavior of series of peripheral substituted cobalt phthalocyanines with consistently changing sulfonated fragments (cobalt phthalocyanine (4-sulfophenyl)ethyl]phenoxy}-tetra-5-(nitro)phthalocyanine (CoPcVII), and cobalt octa-4,5-{4-[1-methyl-1-(4sulfophenyl)ethyl]phenoxy}phthalocyanine (CoPcVIII)) in an aqueous alkaline solution. Comparative analysis of the electrochemical behavior depending on the functional substitution in the macrocycle molecule was carried out. For all the compounds, central metal ion oxidation (Co2+ -> Co3+) and reduction (Co2+ -> Co1+) processes, as well as phthalocyanine ring activity were registered. Based on the occurrence of some peaks in the first scan numbers and the appearance/disappearance of other peaks, a hypothesis regarding the mechanism of electrodeposition of cobalt phthalocyanine derivatives at gold electrodes was formulated. It was shown that the electrodeposition process is generally independent on the nature of the substituent in the phthalocyanine macroring. It was also confirmed that reacting species are adsorbed on the electrode surface without specific diffusion.

A copper complex of tetra-4-(4'-methoxyphenoxy)phthalocyanine was obtained by template synthesis. Its spectral properties in solutions of chloroform, DMF, and sulfuric acid were studied. It has been established that the studied copper phthalocyanine in chloroform solution exists mainly in the monomeric form. The mesomorphism study by the method of polarization optical microscopy showed that the compound is mesogenic, exhibiting a columnar mesophase within a wide temperature range. On cooling, the compound vitrifies with preservation of the mesophase texture. Thin films of individual phthalocyaninate and its mixture with a fullerene derivative (PCBM) were obtained by spin-coating. The film thickness and surface relief were evaluated by atomic force microscopy. The spectral (absorption and fluorescence) and photophysical properties of the films have been studied. It is shown that the presence of photovoltage in individual phthalocyaninate is two times higher than in its composition with PCBM. Over time (after one year), the photovoltaic response of the film based on the individual phthalocyaninate significantly decreased, while in the film with the addition of PCBM it increased three times compared to the initial values ​​for freshly prepared samples. This behavior of photodiodes based on phthalocyanine – fullerene compositions is not typical and was observed for the first time.

Gadolinium and erbium complexes were obtained on the basis of 4-[4-(4-methylphenylazo)phenoxy]phthalonitrile, and the effect of the complex-forming metal on the spectral properties of the resulting compounds was studied.

Novel neodymium phthalocyaninates based on template condensation of 4-[(4-benzyloxy)phenoxy]- or 4-(1-methyl-1-phenylethyl)phenoxyphthalonitriles with neodymium salts were obtained. The most selective preparation of neodymium sandwich complexes was found to occur with neodymium acetate as a template. The spectroscopic properties of neodymium metal complexes synthesized in organic solvents were studied. It was determined sandwich complexes of neodymium forms a mixture of in "blue" and "green" forms in the solution.

A number of phthalonitriles with regularly varying peripheral phenoxyl substituents have been obtained by nucleophilic substitution of the nitro group/bromine atom with fragments of phenol derivatives. Based on these phthalonitriles, magnesium complex of with phthalocyanine ligands of various structures have been synthesized. For such complexes, the role of the nature, location, and number of substituents has been determined when considering the spectral and fluorescent parameters in various solvents. It is shown that, for the metal phthalocyanines under study, the spectral characteristics are largely influenced by the location of the substituent, while the values of the fluorescence quantum yields are influenced by all of the above characteristics.

The synthesis of peripherally and non-peripherally substituted erbium phthalocyanines with cyclohexylphenoxyl or phenylphenoxyl fragments by the template condensation of substituted phthalonitrile and erbium chloride in boiling isoamyl alcohol was studied. The role of the influence of the substituents in the macrocycle on the yield of the product was revealed. The change in the spectra of the synthesized compounds in various solvents was studied.