scholarly journals SYNTHESIS, COORDINATION AND ACID-BASE PROPERTIES OF MESO-DINITROSUBSTITUTED DERIVATIVES OF 5,15-DIPHENYL-β-OCTAALKYLPORPHINE

2018 ◽  
Vol 61 (6) ◽  
pp. 17
Author(s):  
Svetlana G. Pukhovskaya ◽  
Yulia B. Ivanova ◽  
Dmitry A. Erzunov ◽  
Aleksander S. Semeykin ◽  
Sergei A. Syrbu
Keyword(s):  
Spectral Characteristics ◽  
Spectrophotometric Titration ◽  
Basicity Constant ◽  
Acidity Constant ◽  
Electronic Effects ◽  
Acid Base ◽  
Electronic Effects Of Substituents ◽  
Derivatives Of ◽  
Base Properties

Presented work shows results of synthesis and spectrophotometric researches on properties of meso-dinitrosubstituted derivatives of 5,15-diphenyl-β-octaalkylporphyrin nitroderivatives in comparison with 2,8,12,18,3,7,13,17-octaethylporphyrin and 2,3,7,8,12,13,17,18-octaethyl-5,15-dinitroporphyrin. The method of spectrophotometric titration with perchloric acid (for determining the basicity constant) and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was used in order to study the acid-base properties of porphyrins, namely to determine the acidity constant. The spectral characteristics of the ionized forms of 5,15-dinitro-10,20-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporfin-F (I) and 5,15-dinitro-10,20-bis(4-nitrophenyl)-2,8,12,18-tetramethyl-3,7,13,17-tetraethylporphyrin (II) and the corresponding total constants of the acidic (pKa (I) = 6.00 and pKa (II) = 5.27) and the basic (pKb (I) = 19.78 and pKb (II) = 19.83) ionization were provided. The reaction of complexation of porphyrins with zinc acetate was studied by spectrophotometric method in pure acetonitrile and in mixed AN + DBU solvent. The influence of the degree of deformation of the tetrapyrrole macroring, the electronic effects of substituents and the acidity of the medium on the coordination and acid-base properties of porphyrins was analyzed. It was shown that the reactions of formation of metalloporphyrins with anionic porphyrin forms proceed with much higher rates compared to molecular ones, that is accompanied with a decrease in the energy parameters of the reaction. This is evidently due to the absence of energy costs for the deformation and cleaving N-H bonds of the reaction center, as well as the stronger polarization of the molecule, and as a consequence, the higher degree of solvation of anionic forms of porphyrins in the transition state. Thus, the determination of the conditions for the existence of dianionic forms of porphyrins gives grounds for the development of new sensor systems for the recognition and determination of the concentration of metal cations in liquid media due to a sharp increase in the rate of formation of metalloporphyrins in the presence of an organic base.Forcitation:Pukhovskaya S.G., Ivanova Yu.B., Erzunov D.A., Semeykin A.S., Syrbu S.A. Synthesis, coordination and acid-base properties of meso-dinitrosubstituted derivatives of 5,15-diphenyl-β-octaalkylporphine. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 6. P. 17-28

scholarly journals SPECTROPHOTOMETRIC STUDY OF ACID-BASE PROPERTIES OF SPATIAL-DISTORTED DERIVATIVES OF PORPHYRINS IN ACETONITRILE

2018 ◽  
Vol 59 (6) ◽  
pp. 49 ◽  
Author(s):  
Yulia B. Ivanova ◽  
Svetlana G. Puhovskaya ◽  
Nugzar Zh. Mamardashvili ◽  
Oscar I. Koifman
Keyword(s):  
Absorption Spectra ◽  
Molecular Form ◽  
Spectral Characteristics ◽  
Reaction System ◽  
Spectrophotometric Titration ◽  
Spectrophotometric Study ◽  
Acidic Properties ◽  
Acid Base ◽  
Electron Absorption ◽  
Base Properties

Spectrophotometric titration method was used to study the acidic properties of: 5,10,15,20-tetrakis(thienyl-2-yl)-2,3,7,8,12,13,17,18-octaethylporphyrin (I), 5,10,15,20-tetrakis(4’-t-butylphenyl)-2,3,7,8,12,13,17,18-octaethylporphyrin (II), 5,10,15,20-tetrakis(3,5-di-t-butylphe-nyl)-2,3,7,8,12,13,17,18-octaethylporphyrin (III), 5,10,15,20-tetraphenyl-2,3,7,8,12,13,17,18-octaethylporphyrin (IV), 5,15-bis(4’-methoxyphenyl)-10,20-bis(4-nitro-phenyl)-2,8,12,18-tetrame-thyl-3,7,13,17-tetraarylporphyrin (V), 5,15-bis(4’-methoxyphenyl)-10,20-diphenyl-2,3,7,8,12,13, 17,18-octaethylporphyrin (VI), 5,15-bis(4’-methoxyphenyl)-2,8,12,18-tetramethyl-3,7,10,13,17,20-hexaethylporphin (VII), 5,10,15,20-tetrakis(4’-methoxyphenyl)-2,3,7,8,12,13,17,18-octaethylpor-phyrin (VIII) in the presence of a deprotonated agent, 1,8-diazabicyclo[5.4.0] undec-7-ene, in acetonitrile. Under deprotonation two families of spectral curves in the absorption spectra, having its own system of isobestic points, are formed. Electron absorption spectrum of molecular form transforms gradually into the spectrum of the final form of dianion with titrant concentration increase. Determination of the coordinates of the inflection (and the corresponding concentration of DBU) on the titration curve  allowed us to distinguish two areas in the electron absorption spectra of the reaction system, which are likely belong to the first and second steps of deprotonation, namely, to the formation of mono- and dianionic forms (HP–  and P2–) of the compound. Spectral characteristics of the ionized forms and combined ionization constant for the first and second steps (lgКа1 and lgКа2) were revealed. At the first step in the order of decreasing acidic properties of the ligands the compounds form a series of: III< V< VIII< VI < VII< II< IV < I; at the second step in decreasing order of the acidic properties of the ligands the compounds form a series of:.III < V < VI < II <VIII< VII < IV < I. The effect of structural and electronic properties of substituents on acid-base properties of porphyrins is analyzed. Thus, chemical modification of the macrocycle can lead to direct changes in acid-base properties of supramolecular macroheterocyclic ligands and can be a powerful tool to control the reactivity of compounds of the porphyrins class.

Spectrophotometric study of the acid-base and optical properties of the 5-bromo and 5-chloro derivatives of 2-(2-pyridylazo)-5-(diethylamino)phenol (BrPADAP, ClPADAP) and their complexation equilibria with zinc(II) ions

1982 ◽  
Vol 47 (10) ◽  
pp. 2676-2691 ◽  
Author(s):  
Miroslav Macka ◽  
Vlastimil Kubáň
Keyword(s):  
Equilibrium Constants ◽  
Spectrophotometric Study ◽  
Graphical Analysis ◽  
Alkaline Media ◽  
Acid Base ◽  
Ethanol Medium ◽  
Triton X ◽  
Mixed Water ◽  
Derivatives Of

The optical and acid-base characteristics of BrPADAP and ClPADAP were studied in mixed water-ethanol and water-DMF media and in 10% ethanol medium in the presence of cationic, anionic and nonionic tensides. The composition, optical characteristics, molar absorption coefficients and equilibrium constants of the ML and ML2 complexes with zinc(II) ions were found by graphical analysis and numerical interpretation of the absorbance curves by the modified SQUAD-G program. Optimal conditions were found for the spectrophotometric determination of Zn(II) in the presence of 0.1% Triton X-100 or 1% Brij 35 in alkaline media with pH = 6.5-10. BrPADAP and ClPADAP are the most sensitive reagents (ε = 1.3-1.6 . 105 mmol-1 cm2 at 557 and 560 nm, respectively) for the determination of zinc with high colour contrast of the reaction (Δλ = 104 nm) and selectivity similar to that for the other N-heterocyclic azodyes (PAN, PAR, etc.).

scholarly journals The reactivity of aromatic and heterocyclic derivatives of hydrazine. Vіі. The acid-base properties of substituted 5,7-dichloro-9-hydrazine acridine

2016 ◽  
Vol 0 (1(85)) ◽  
pp. 12-14
Author(s):  
A. O. Deviatkina ◽  
O. M. Svechnikova ◽  
S. V. Kolisnyk ◽  
N. P. Kobzar ◽  
A. F. Vinnyk
Keyword(s):  
Acid Base ◽  
Heterocyclic Derivatives ◽  
Derivatives Of ◽  
Base Properties

Toward novel sulphur-containing derivatives of tetraazacyclododecane: synthesis, acid–base properties, spectroscopic characterization, DFT calculations, and cadmium(ii) complex formation in aqueous solution

2020 ◽  
Vol 44 (20) ◽  
pp. 8337-8350 ◽  
Author(s):  
Marianna Tosato ◽  
Marco Verona ◽  
Riccardo Doro ◽  
Marco Dalla Tiezza ◽  
Laura Orian ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Complex Formation ◽  
Dft Calculations ◽  
Spectroscopic Characterization ◽  
Acid Base ◽  
Derivatives Of ◽  
Base Properties

New sulphur derivatives of cyclen, with potential complementary properties with respect to known compounds, have been synthesized and studied.

Spectrofluorimetric Study of the Inclusion Complex of 7-Hydroxymethylnalidixic Acid with γ-Cyclodextrin in Aqueous Solution

1997 ◽  
Vol 51 (5) ◽  
pp. 684-688 ◽  
Author(s):  
Isabel Durán-Merás ◽  
Arsenio Muñoz De La Peña ◽  
Francisco Salinas ◽  
Isabel Rodríguez Cáceres
Keyword(s):  
Aqueous Solution ◽  
Inclusion Complex ◽  
Formation Constant ◽  
Spectral Characteristics ◽  
Stoichiometric Ratio ◽  
Acid Base ◽  
Method Of Determination ◽  
Cyclodextrin Cavity ◽  
Complexation Process

A fluorimetric study on the spectral characteristics and acid-base behavior of 7-hydroxymethylnalidixic acid has been performed. The host–guest complexation process between γ-cyclodextrin and 7-hydroxymethylnalid ixic acid has also been investigated by fluorescence spectroscopy. Scatchard and Benesi-Hildebr and methods have been applied to determine the stoichiometry of the complex, and a 1:1 stoichiometric ratio has been established. A K1 = 118 ± 25 M−1 formation constant has been calculated for the inclusion complex, by using the changes produced on the fluorescence of 7-hydroxymethylnalid ixic acid, when it is included on the hydrophobic cyclodextrin cavity. A fluorimetric method of determination of 7-hydroxymethylnalid ixic acid, in γ-cyclodextrin aqueous solution, has been proposed. The analytical parameters and detection and quantification limits of the method have been determined.

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