Solubility In Chloroform Research Articles

Valorization of hemicellulose waste streams for moisture barrier coatings and hydrophobic films

Replacing plastics with renewable and environmentally friendly substitutes is becoming ever more critical as we begin to realize the consequences of their negative impacts on the environment. Plant polysaccharides are the most abundant biopolymers on Earth, and hemicelluloses like xylan that are enriched in many agro-industrial waste streams have vast potential as eco-friendly building blocks for polymer science and engineering. However, xylan is one of the less studied natural polymers for applications that are relevant to the synthetic plastics and polymeric materials markets. Hemicellulose isolated from viscose and Lyocell fiber mills is largely seen as a waste product due to difficulties arising from the potential for structural heterogeneity and its lack of solubility after enrichment. In this work, we developed a strategy to valorize hemicellulose by functionalization with octyl isocyanate to achieve solubility and thermoplastic/hydrophobic properties. Xylan isolated from dissolving pulp waste streams was successfully functionalized with octyl isocyanate in DMSO at an estimated 79% hydroxyl conversion. Reaction parameters, including temperature, time, and stoichiometry were optimized for each reaction. The resultant carbamates of xylan oligo- and monosaccharides have good solubility in chloroform and impressive hydrophobic film forming properties yet retain the composability properties desired for renewable materials that are envisioned to enter the circular bioeconomy. Functionalization of xylan with an aliphatic chain through formation of an aliphatic carbamate is not expected to harbor the same toxicity or carcinogenic characteristics as the reactive isocyanate it is derived from, and thus should not inherently restrict these materials for use in diverse packaging applications. These modified physical properties show that xylan from agro-industrial waste streams has considerable potential to replace petroleum-based feedstocks in the existing packaging industry. In the future, we will continue to further develop strategies for valorization of these materials.Graphical

Asymmetrical Diketopyrrolopyrrole Derivatives with Improved Solubility and Balanced Charge Transport Properties.

The diketopyrrolopyrrole (DPP) unit represents one of the building blocks more widely employed in the field of organic electronics; in most of the reported DPP-based small molecules, this unit represents the electron acceptor core symmetrically coupled to donor moieties, and the solubility is guaranteed by functionalizing lactamic nitrogens with long and branched alkyl tails. In this paper, we explored the possibility of modulating the solubility by realizing asymmetric DPP derivatives, where the molecular structure is extended in just one direction. Four novel derivatives have been prepared, characterized by a common dithyenil-DPP fragment and functionalized on one side by a thiophene unit linked to different auxiliary electron acceptor groups. As compared to previously reported symmetric analogs, the novel dyes showed an increased solubility in chloroform and proved to be soluble in THF as well. The novel dyes underwent a thorough optical and electrochemical characterization. Electronic properties were studied at the DFT levels. All the dyes were used as active layers in organic field effect transistors, showing balanced charge transport properties.

Development of heat-assisted in-situ solvent formation liquid phase microextraction followed by derivatization for the simultaneous extraction of aliphatic amines from wastewater samples prior to gas chromatography-mass spectrometry

Herein, a cost-effective, rapid, and selective liquid phase microextraction procedure has been developed for the extraction of some aliphatic amines from sewage samples. The method was based on in-situ formation of chloroform as an extraction solvent into the sample solution followed by derivatization by butylchloroformate prior to gas chromatography- mass spectrometry. Chloroform is formed by the reaction of chloral hydrate and sodium hydroxide. The extraction procedure was accelerated by heating. Also heating decreases chloroform solubility in aqueous solution. To improve the analytical signals, derivatization of the analytes is done by butylchloroformate. The effect of major parameters on the extraction efficiency were studied and optimized. Under the optimized conditions, enrichment factor and extraction recovery were in the ranges of 259–296 and 78–89 %, respectively. Low limits of detection (0.08–0.12 ng mL−1) and quantification (0.28–0.41 ng mL−1), wide linear ranges, and relative standard deviations less than 6 % for intra −and inter-day precisions were acceptable. Lastly, the mentioned method was successfully performed to determine aliphatic amines in wastewater samples.

Modulation of Phase Separation Morphology by Configuration Engineering in Bulk Heterojunction Organic Solar Cells

For bulk‐heterojunction organic solar cells (OSCs), molecular structure design to control molecular stacking is crucial to obtain ideally phase‐separated morphology and high device performance. Herein, the investigation focuses on two polythiophene‐quinoxaline (PTQ) derivatives (PTQ8 and PTQ10) blended with Y6, utilizing coarse‐grained molecular dynamics simulations based on the Lennard–Jones static potential (LJSP) method. The study reveals that the diminished photovoltaic efficiencies of PTQ8:Y6 blends, compared to PTQ10:Y6 blends, are not solely attributed to reduced driving forces. The introduction of fluorine‐substituted sites in the thiophene group of PTQ polymer is identified as a significant factor. This alteration causes PTQ polymers in PTQ8:Y6 blends to coil, compromising the crystalline structure. PTQ8's bifluorine group induces a repulsive effect on the quinoxaline group, leading to a coiled‐chain structure that hinders chain stacking. Conversely, PTQ10 exhibits a straighter chain conformation. Additionally, PTQ8's high solubility in chloroform prevents effective aggregation, further impeding suitable morphology formation. Coarse‐grained simulations employing LJSP prove effective in precisely exploring the morphology of OSCs, offering crucial insights for materials in this field.

Molecular Docking, Synthesis and Antimicrobial Evaluation of 4-[(3 hydroxybenzalidene)amino]antipyrine and its Copper Complex

The synthesis and characterization of Schiff base-containing transition metal complexes have gained increasing importance due to their catalytic roles in various reactions and their biological activities. These metal complexes have become crucial in drug design, leading to a growing interest in metal-based drugs. The study aimed to synthesize copper metal complex with a new Schiff base ligand 4-[(3-hydroxybenzalidene)amino]antipyrine derived from 4-aminoantipyrine and 3-hydroxybenzaldehyde, as well as evaluate their antimicrobial activity against gram positive and gram-negative bacterial strains. The ligand and its copper complex were assessed for antimicrobial activity against gram-positive and gram-negative strains utilizing disc diffusion and broth dilution methods. Spectroscopic techniques (UV-Vis, FT-IR, XRD, and EDXRF), solubility tests, and elemental analysis were employed to investigate the ligand and copper complex. The ligand displayed high insolubility in various solvents but had limited solubility in chloroform and methyl chloride. The FTIR spectrum of the Schiff base reveals the presence of aromatic hydrocarbons, imine (C=N), hydroxyl (-OH), secondary amine (C-N), carbonyl (C=O), and vibrations associated with C-O and C-C bonds, reflecting its molecular structure. In the EDXRF analysis, a prominent peak at 7.80 keV corresponding to copper was detected, indicating that copper is the most abundant element found in the ligand. XRD analysis demonstrated distinct crystal structures for both the ligand and its copper complex. The UV-Vis spectra of the ligand exhibited an absorption peak at a UV lambda max of 220 nm, indicating a π→π* transition. In contrast, the absorption peaks observed in the copper complex indicated different transitions compared to the Schiff base. The MIC results indicated the copper complex's stronger antimicrobial activity than the Schiff base against tested bacteria. Molecular docking studies showed that the interaction energies of the synthesized compounds, particularly the ligand and copper complex, surpassed that of the well-known anti-diabetic drug, metformin.

Bis(chlorido)tin(IV)meso‐substituted Porphyrins‐Characterization and Solubility

AbstractInvestigation of the solubility behavior of para‐substituted (H, Me, t‐Bu, n‐Bu) meso‐tetraarylporphyrins as well as meso‐tetraalkylporphyrins (Me, n‐Pr, n‐Bu) were performed. An increase of solubility in chloroform and benzene is detected according to the higher functionality in para position of the phenyl ring for meso‐tetraarylporphyrins or in meso position on meso‐tetraalkylporphyrins. Furthermore, the series of bis(chlorido)tin(IV) meso‐tetraarylporphyrin and bis(chlorido)tin(IV) meso‐tetraalkylporphyrin was investigated via UV/Vis spectroscopy, 119Sn‐NMR and single crystal X‐ray diffraction.

Vinyl-Flanked Diketopyrrolopyrrole Polymer/MoS2 Hybrid for Donor–Acceptor Semiconductor Photodetection

Polymers containing the 1,4-diketo-pyrrolo[3,4-c]pyrrole (diketopyrrolopyrrole, DPP) unit are highly desirable for optoelectronic devices. However, the requirements for the substituents flanking the DPP unit at the 3,6-positions are limited to aryl groups due to the lack of synthetic methods to prepare other substituted DPP. This paper describes the synthesis, characterization, and application of the first vinyl-flanked DPP polymers: DPP-vinyl-thiophene-vinyl (PDPPVTV) and DPP-vinyl-thiophene-thiophene (PDPPVTT). The position of the vinyl group is varied to determine its effect on the physical and optoelectrical properties of the polymers. The semicrystalline polymers record moderate molecular weights (Mn ∼ 25–30 kDa), good solubility in chloroform, and high thermal stabilities (Td onset ∼ 400 °C). Both polymers have broad absorption bands in the solid state (abs λmax ∼ 800 nm) that extend into the near-infrared (NIR) region (900–1000 nm). PDPPVTT has two orders of magnitude higher hole mobility than PDPPVTV (0.25 vs 0.0018 cm2 V–1 s–1) and is used as a coating material in a MoS2 FET device. The PDPPVTT/2D MoS2 hybrid device shows higher photoresponsivity in the NIR region (103 A/W at 800 nm and 102 A/W at 1050 nm) than the pristine MoS2 photodetector (102 A/W at 800 nm and 0 A/W at 1050 nm).

Preparation and performance of soluble N-heterocyclic poly(aryl ether ketone)s with enhanced thermal resistance

The novel poly(aryl ether ketone)s embodying bis-phthalazinone units (PBPEK-Ps) with enhanced solubility and thermal resistance are incorporated by one-pot condensation polymerization. The impacts of solvents on the copolymerization behavior of PBPEK-Ps have been evaluated. The structure characteristics of polymers are identified through infrared absorption spectrum and nuclear magnetic resonance spectra. PBPEK-Ps exhibit favorable thermo-stability and possess glass transition temperatures ranging from 256 to 305 °C. Simultaneously, PBPEK-Ps perform storage modulus above 3.46 GPa with the storage modulus preservation at 250 °C up to 58% and the tensile strength over 111 MPa, exhibiting excellent thermo-resistance and mechanical properties. Moreover, the rigid twisted units and pendant phenyl groups endow PBPEK-Ps with excellent solubility in chloroform and N-methylpyrrolidone, and a controllable contact angle in the range of 79.5° – 91.0°. And PBPEK-Ps possess favorable insulation performance.

Synthesis and characterization of paramylon propionate-graft- poly(lactic acid) and paramylon propionate-graft-poly(ε-caprolactone)

Paramylon propionate-graft-poly(L-lactic acid) (PaPr-g-PLA) and paramylon propionate-graft-poly(ε-caprolactone) (PaPr-g-PCL) were synthesized by grafting L-lactide and ε-caprolactone to the residual hydroxy group of paramylon propionate (degree of substitution (DS) of 1.6 or 2.0). The chemical structures of the graft copolymers were characterized by GPC, NMR, and FT-IR measurements. The molecular weight of the copolymers was 2.52–3.11 × 105 and the degree of polymerization of grafted side-chains was determined to be around 10. Melt-pressed films were formed from all copolymers but solvent-cast films were brittle and defected. The terminal hydroxy groups of the grafted PLA or PCL side-chains were subsequently acetylated. The acetylated graft copolymers showed good solubility in chloroform and formed self-standing uniform solvent-casted films as well as melt-pressed films. The decomposition temperature of the acetylated graft copolymers was 350 °C, which was 50 °C higher than that of nonacetylated copolymers, indicating that terminal acetylation dramatically improved the thermal stability of the copolymers. The mechanical properties of the films of the acetylated copolymers were investigated and discussed.

Determination and correlation of solubility and solution thermodynamics of 1, 2-diphenylethane in different pure solvents

The correlation of solubility and solution thermodynamics of 1,2- diphenylethane in different pure solvents has been studied. The mole fraction solubilities of 1, 2-diphenylethane in acetone, chloroform, dichloromethane, and ethanol increase with temperature. The mole fraction solubility in acetone, chloroform and dichloromethaneare much higher than that in ethanol and the mole fraction solubilities in chloroform and dichloromethane are higher than that in acetone. The solubility data were well correlated by the modified Apelblat,the semi-empirical Buchowski-Ksiazczak λh equation, and the ideal solution equation.The enthalpy, entropy and apparent free Gibbs energy of solution in different solvents were calculated. The dissolving process of 1,2-diphenylethane was endothermic, entropy-driving and not spontaneous.

Solubility measurement and thermodynamic modeling of carbamazepine (form III) in five pure solvents at various temperatures

In this work, the solubilities of carbamazepine (CBZ) (form III) in ethyl acetate, methyl acetate, ethylene glycol, chloroform and cyclohexylamine were determined by laser monitoring techniques at pressure above sea level, and the solubility data of CBZ (form III) in different pure solvents were fitted by the Modified Apelblat model and λh model. The result shows that the solubility of CBZ (form III) in five solvents increases as temperature rises, and the solubility in chloroform was the largest. The experimental solubility values of CBZ (form III) in ethyl acetate, methyl acetate, chloroform and cyclohexylamine were in better agreement with the simulated fitting values of the λh model. For ethylene glycol, the σ value was much larger than the other four solvents, and it can be seen from the λh model that ethylene glycol was closer to the ideal solution system than the other four solvents.

Effect of Bridgehead Methyl Substituents on the Gas Permeability of Tröger's-Base Derived Polymers of Intrinsic Microporosity.

A detailed comparison of the gas permeability of four Polymers of Intrinsic Microporosity containing Tröger’s base (TB-PIMs) is reported. In particular, we present the results of a systematic study of the differences between four related polymers, highlighting the importance of the role of methyl groups positioned at the bridgehead of ethanoanthracene (EA) and triptycene (Trip) components. The PIMs show BET surface areas between 845–1028 m2 g−1 and complete solubility in chloroform, which allowed for the casting of robust films that provided excellent permselectivities for O2/N2, CO2/N2, CO2/CH4 and H2/CH4 gas pairs so that some data surpass the 2008 Robeson upper bounds. Their interesting gas transport properties were mostly ascribed to a combination of high permeability and very strong size-selectivity of the polymers. Time lag measurements and determination of the gas diffusion coefficient of all polymers revealed that physical ageing strongly increased the size-selectivity, making them suitable for the preparation of thin film composite membranes.

Preparation and Electrochemical and Optical Properties of α‐Alkoxyphthalocyanines with β‐Pyridylthio Groups

Phthalocyanines (Pcs) 5a‐Mg, 5b‐Mg, 6a‐Mg, and 6b‐Mg with eight alkoxy groups at α‐positions and 2‐ or 4‐pyridylthio groups at the β‐positions, were prepared from 3,6‐dialkoxy‐4,5‐dipyridylthiophthalonitriles. Magnesium complexes 5a‐Mg, 5b‐Mg, and 6a‐Mg were treated with trifluoroacetic acid to produce free‐base compounds 5a‐2H, 5b‐2H, and 6a‐2H. In the UV/Vis spectra, Q‐band absorption of Mg and free‐base Pcs appeared near 760 nm and 780 nm, respectively, in chloroform and 745 nm and 760 nm, respectively, in methanol. Emission spectra of these Pcs showed small Stokes shifts in chloroform and methanol. Reactions of 5a‐Mg, 5b‐Mg, and 5b‐2H with methyl iodide produced the corresponding Pcs 7a‐Mg, 7b‐Mg, and 7b‐2H with methyl pyridinium groups, respectively. After methylation of the pyridine nitrogen, the Pcs were moderately soluble in water but had little solubility in chloroform. The UV/Vis and emission spectra of methylated Pcs 7a‐Mg, 7b‐Mg, and 7b‐2H were obtained in methanol and water. Photobleaching of diphenylisobenzofuran (DPBF) was examined in methanol in the presence of Pcs 7b‐Mg and 7b‐2H, and was monitored by UV/Vis spectroscopy.

Synthesis and Characterization of Benzothiadiazole and Dicyanovinylindandione Based Small-Molecular Conjugated Materials and Their Photovoltaic Properties

A series of non-fullerene small molecules (BT-T-IDC and BT-T-tB-IDC) with the architecture of A1-π-A2-π-A1 (acceptor 1-π-acceptor 2-π-acceptor 1), electron-deficient benzothiadiazole (BT) used as the core (A2), electron-rich thiophene used as the π-bridge (π), and electron-deficient dicyanovinylindandione (IDC) or t-butyl substituted IDC used as end groups (A1), have been synthesized. IDC groups are widely used as the acceptor unit due to the strong electron-withdrawing property that can lead to deep LUMO energy levels. Materials showed good thermal stability with the onset decomposition temperature (Td) upon 310 °C at 5 wt% loss. BT-T-tB-IDC showed better solubility in chloroform and chlorobenzene than that of BT-T-IDC due to t-butyl groups on the IDC. The HOMO/LUMO energy levels of BT-T-IDC and BT-T-tB-IDC were −5.60/−3.90 and −5.71/−3.87 eV, respectively. Organic solar cell based on PBDBT-T (poly[(2,6-(4,8-bis (5-(2-ethylhexyl) thiophen-2-yl)-benzo [1,2-b:4,5-b′] dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl) benzo[1′,2′-c:4′,5′-c′] dithiophene-4,8-dione))])) as the donor and BT-T-IDC as the acceptor showed low power conversion efficiency (PCE) of 0.06% due to poor solubility. However, the PCE of the device based on BT-T-tB-IDC showed a better PCE of 1.55%.

A High‐Performance Non‐Fullerene Acceptor Compatible with Polymers with Different Bandgaps for Efficient Organic Solar Cells

Owing to their good polymer compatibility, fullerene derivatives, such as PC61BM and PC71BM, have been the dominant electron acceptors to pair with various polymer donors in polymer solar cells (PSCs). The recent surge of non‐fullerene materials leads to several high‐performance molecular acceptors. Despite their high performance in a given polymer/acceptor system, the generality of these acceptors, i.e., their compatibility with different donor polymers remains uncertain. Here, a high‐performance small molecule acceptor (SMA), BTTIC, is designed and synthesized to combine with three polymers with different bandgaps, namely J71 (1.92 eV), PBDB‐T (1.80 eV), and PTB7‐Th (1.58 eV). Complementary absorption, compatible energy levels, and particularly the favorable morphologies between BTTIC and the three polymers enable high power conversion efficiencies (PCEs), which are 12.8%, 13.2%, and 10.4% for J71:BTTIC‐, PBDB‐T:BTTIC‐, and PTB7‐Th:BTTIC‐based PSCs, respectively, significantly higher than the PCEs of the fullerene‐ or other non‐fullerene‐based counterparts. Moreover, another famous p‐type polymer donor PffBT4T‐2OD, which shows poor solubility in chloroform and has not yet been studied in non‐fullerene PSCs, is also investigated. Processing by dissolving PffBT4T‐2OD and BTTIC in boiling chloroform enables PffBT4T‐2OD:BTTIC‐based PSCs with a PCE of 10.18%, which is significantly higher than that of PSCs (4.78%) before using boiling chloroform processing. The good compatibility of BTTIC with polymers that have either large, moderate, or small bandgaps makes it a promising non‐fullerene acceptor for next‐generation non‐fullerene PSCs.

Natural Bitumens: Physicochemical Properties and Production Technologies

The physicochemical parameters and the extraction technologies of natural bitumens—solid or viscous natural materials that are the products of hypergenic, phase-migratory, contact-metamorphic, and other natural transformations of oil—were analyzed. The separation of bitumens is based on their physicochemical properties, the most important of which are solubility in chloroform, oil content, specific gravity, coking behavior, Mohs hardness, group composition, and consistency. It was shown that the physicochemical properties of natural bitumens and black and oil shales, their hydrocarbon composition, and the concentrations and ratios of their ore components depend on the initial organic matter, the litho-facial conditions of its burial, and the subsequent accumulation and destruction, that is, on the geological history of sedimentary basins. To improve the efficiency of further development of natural bitumen deposits, it was proposed to introduce a highly efficient integrated technology for developing hard-to-recover reserves, the most important elements of which are the application of thermal effects using various heat sources, horizontal drilling, and hydraulic fracturing.

Effect of heat treatment on wood chemical composition, extraction yield and quality of the extractives of some wood species by the use of molybdenum catalysts

The effect of heat treatment and the presence of some molybdenum catalysts on the amount of extractives in Populus nigra, Larix decidua, Paulownia tomentosa, Castanea sativa and Quercus frainetto wood were studied. There are an increase in the amount of lignin and extractives and a decrease in the amount of holocellulose following thermo-treatment, in the treatment temperature range. Autoclave treatment of wood with water in the presence of some molybdenum catalysts can increase the amount of extracts, but it reduces solubility. Soxhlet extraction of wood with ethanol/toluene mixture in the presence of H3PMo12O40 increases the amount of extractives and their solubility in chloroform, while in the presence of MoO3 only the solubility of extractives increases. GC–MS analysis of insoluble fraction showed the presence of myo-inositol and some simple carbohydrates, mainly ribose, xylose and glucose. GC–MS analysis of soluble fraction showed the presence of long-chain acids and fatty acid esters of 10–20 carbon atoms, mainly decanoic acid, hexadecanoic acid and octadecanoic acid, which can be a source of fatty acids for biodiesel production.

Photogeneration of Singlet Oxygen by Tetra(p-Hydroxyphenyl)porphyrins Modified with Oligo- and Polyalkylene Oxides

Mono- and diethylene oxide derivatives of tetra(p-hydroxyphenyl)porphyrin (THPP) with different conformation states are synthesized. These compounds exhibit high photosensitization activity in the generation of singlet oxygen in organic and aqueous (in the solubilized state) phases. It is shown that introducing ethylene oxide moieties into the hydroxyphenyl substituents of THPP increases its solubility in chloroform. In addition, the activity of singlet oxygen 1Δg generation in the reaction of anthracene photooxidation by THPP tetra derivatives in chloroform, where the ethylene oxide fragments are introduced into two phenyl rings and hexadecyl fragments are introduced into another two, is higher than the activity of mono- and di-modified THPP molecules with enthylene oxide molecules at one hydroxyphenyl cycle. The activity of tetra-substituted porphyrin in chloroform, however, is comparable to that of nonsubstituted tetraphenylporphyrin, considered to be one of the most active photosensitizers. The produced ethylene oxide derivatives of THPP are solubilized with pluronic F-127 (triblock copolymer of ethylene- and propylene-oxides)—one of the least toxic and effective polymeric detergents—forming water-soluble forms of the respective porphyrins. It is established that the pluronic solubilization capability (the lowest molar concentration of pluronic required for the complete transfer of porphyrin of a particular molar concentration dissolved in organic phase to the water-soluble form) is higher for asymmetrical mono- and di-derivatives of the THPP than for symmetric tetra-substituted THPP. It is shown that the activity of the solubilized water-soluble form of mono- and tetra-derivatives in tryptophan photoxidation is higher than that of unsubstituted THPP and is comparable to the activity of tetraphenylporphyrin.

Cytotoxicity induced by the mixture components of nickel and poly aromatic hydrocarbons.

Although particulate matter (PM) is composed of various chemicals, investigations regarding the toxicity that results from mixing the substances in PM are insufficient. In this study, the effects of low levels of three PAHs (benz[a]anthracene, benzo[a]pyrene, and dibenz[a,h]anthracene) on Ni toxicity were investigated to assess the combined effect of Ni-PAHs on the environment. We compared the difference in cell mortality and total glutathione (tGSH) reduction between single Ni and Ni-PAHs co-exposure using A549 (human alveolar carcinoma). In addition, we measured the change in Ni solubility in chloroform that was triggered by PAHs to confirm the existence of cation-π interactions between Ni and PAHs. In the single Ni exposure, the dose-response curve of cell mortality and tGSH reduction were very similar, indicating that cell death was mediated by the oxidative stress. However, 10μM PAHs induced a depleted tGSH reduction compared to single Ni without a change in cell mortality. The solubility of Ni in chloroform was greatly enhanced by the addition of benz[a]anthracene, which demonstrates the cation-π interactions between Ni and PAHs. Ni-PAH complexes can change the toxicity mechanisms of Ni from oxidative stress to others due to the reduction of Ni2+ bioavailability and the accumulation of Ni-PAH complexes on cell membranes. The abundant PAHs contained in PM have strong potential to interact with metals, which can affect the toxicity of the metal. Therefore, the mixture toxicity and interactions between diverse metals and PAHs in PM should be investigated in the future.

SYNTHESIS AND OPTICAL PROPERTIES OF CAMPHOR-SABSTITUTED TETRAPYRAZINOPORPHYRAZINES

The synthesis of the complexes of Cu, Ni, Co, Pd, Sn, Hg of 1',7',7'-trimethylbicyclo[2.2.1]heptano-[2',3'-b]-2,3-pyrazinoporphyrazine for new materials for variety of potential applications is described. Metallic complexes were synthesized by the template cyclotetramerization of dicarbonitrile with metal chlorides at temperature 140-150 ºС for 20 min. Ammonium molybdate tetrahydrate was used as a catalyst. The products were purificated by chromatography on silica gel (eluent -chloroform). Complexes of Pd, Sn and Hg were synthesized for the first time. The metallocomplexes of camphor-substituted tetrapyrazinoporphyrazine are crystalline substances of dark blue color, not fusible up to 300 ° C, which have good solubility in chloroform, toluene, ethanol, acetone, DMF, acetic and trifluoroacetic acids. The chemical structures of the complexes of Cu, Ni, Co, Pd, Sn, Hg of 1',7',7'-trimethylbicyclo[2.2.1]heptano-[2’,3’-b]-2,3-pyrazinoporphyrazine obtained in this study were characterized by proton nuclear magnetic resonance and mass spectrometry. The absence of impurity signals in the 1H NMR spectra indicates a high degree of purity of the compounds obtained. For copper, nickel and cobalt complexes, a good correlation was found between the experimental and literature data on the chemical shifts of protons in 1H NMR spectra. Optical properties of the synthesized complexes were studied. The electronic absorption spectra of the complexes in their chloroform, DMF, acetic acid and sulfuric acid solutions were obtained. In organic solvents the typical B band (Soret band, around 400 nm) and Q band (in 600-700 nm region) of phthalocyanines were identified in this study. Complexes of Pd, Sn and Hg in their sulfuric acid solutions are non-stable. The influence of the chemical structure of metalic complexes and solvents on the optical properties was studied. Emission properties of the synthesized complexes of Pd and Hg in their chloroform and DMF solutions were analyzed. Hg-porphyrazine has very intensive fluorescence. The solution has blue color and red fluorescence at common condition.Forcitation:Kuvshinov G.V., Ziyadova T.M., Kuvshinova S.A., Koifman O.I. Synthesis and optical properties of camphor-sabstituted tetrapyrazinoporphyrazines. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 4. P. 60-67.