E. V. Antina

Regularities of the formation of binuclear homo- and heteroleptic complexes of d metals with 3,3′-bis(dipyrrolylmethenes) in DMF

The reactions of seven symmetrically alkylated tetradentate ligands 3,3′-bis(dipyrrolylmethenes) (H2L) with d-metal acetates (M(AcO)2) in DMF solutions at 298.15 K were studied by spectrophotometry. Helicands H2L were found to be structurally preorganized to form stable binuclear homoleptic two-helix helicates [M2L2] with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II) acetates. The coordination of the ligands by the metal ions included consecutive stages of formation of the heteroleptic [M2L(AcO)2] and homoleptic [M2L2] complexes. The [M2L(AcO)2] complexes were spectrally revealed in solutions containing a ligand excess (cH2L / cM(AcO)2 > 1). An increase in the salt concentration shifted the system of equilibria to the homoligand product [M2L2]. The thermodynamic constants of the reactions increased in the series of complexing agents: Cu(II) < Cd(II) < Hg(II) < Ni(II) < Co(II) < Zn(II). An analysis of the data on the thermodynamic constants of [M2L2] helicate formation in solutions and the earlier obtained results of the IR and 1H NMR studies of the hydrobromic salts of the ligands (H2L · 2HBr) showed that the key regularities of the influence of the structural factors on the coordination properties of the ligands were in an increase in the stability of the [M2L2] complexes with an increase in the basicity of the ligands.

Characteristic features of formation, synthesis, and properties of binuclear zinc(II) helicates with alkyl-substituted 3,3′-bis(dipyrrolylmethenes)

On the basis of spectrophotometric studies, it was demonstrated that complexation of hydrobromides of seven alkylated 3,3′-bis(dipyrrolylmethenes) (H2L · 2HBr) with zinc(II) acetate dihydrate in DMF (298.15 K) includes successive steps of formation of binuclear helicates of two types: [Zn2(AcO)2L] (heteroleptic single-helix complex) and [Zn2L2] (homoleptic double-helix complex). An increase in the degree of alkylation of the pyrrole rings of the ligands from 4 to 10 methyl groups induces an increase of overall complexation constants from 7.60 to 13.73. The synthesis of helicates [Zn2L2] was described. The products were studied by elemental analysis and IR, 1H NMR, U/Vis, and fluorescence spectroscopy. The effect of the helicand structure and the solvent nature on the chromophore and fluorescence properties of [Zn2L2] was discussed. The kinetic stability of zinc(II) with decamethyl-substituted 3,3′-bis(dipyrrolylmethene) in HCl-DMF medium was estimated.

Thermal oxidative degradation of the functionally substituted 2,2′-dipyrrolylmethenes hydrobromides and difluoroborates

Thermal oxidative decomposition of samples of crystalline hydrobromide and borofluoride complexes (BODIPY) of a series of 2,2′-dipyrrolylmethenes (HL) was studied by means of thermogravimetry in an atmosphere of air oxygen. An increase in the degree and symmetry of substitution, aromaticity, and the length of the substituents in 4,4′-positions of the pyrrole ligand rings increases stability of the BODIPY-dyes to oxidative degradation. A comparative analysis of the influence of structural factors on the thermolability of hydrobromdes (HL·HBr), d-metal (ML2) and boron(III) complexes with 2,2′-dipyrrolylmethenes was carried out.

Kinetics of the Dissociation of Transition Metal Complexes with α,α-Dipyrrolylmethene in Acetic Acid–Benzene as a Binary Proton-Donating Solvent

The kinetics of the dissociation of Co(II), Ni(II), and Zn(II) complexes with 4,4′-dibutyl-3,3′,5,5′-tetramethyldipyrrol-2,2′-ylmethene was studied in acetic acid–benzene as a binary proton-donating solvent. The metal nature was found to affect the kinetic parameters of the process. Assumptions were made about the limiting step of the process and the effectiveness of d metal ions in the template synthesis of porphyrins from dipyrrolylmethenes.

Thermochemical characteristics of the near surroundings of tetraphenylporpffln in benzene, pyridine and carbon tetrachloride

Abstract A new approach which allows the solvation surroundings of macrocyclic molecules to be simulated is proposed on the basis of thermogravimetric data. For the first time the compositions are determined of saturated solvates of tetraphenylporphin (H 2 TPP) with benzene, pyridine and carbon tetrachloride: H 2 TPP· 16C 6 H 6 , H 2 TPP· 18C 5 H 5 N and H 2 TPP·16CCl 4 . The energetic parameters of the interparticle interactions in the near solvation surroundings of H 2 TPP are characterized. A method is proposed for the evaluation of the change in enthalpies of solvation of macrocyclic molecules based on the values of the heats of evaporation.

Comparative analysis of physicochemical properties of dinuclear zinc(II) helicates with 2,2′-, 2,3′-, and 3,3′-bis(dipyrromethenes)

The effect of the attachment position of a methylene spacer in 2,2′-, 2,3′-, and 3,3′-bis(dipyrromethene) N4-ligands (H2L) on physicochemical properties of their dinuclear homoleptic helicates [Zn2L2], such as specific features of their molecular structure, luminescence spectral characteristics, lability in acid solutions, and thermal stability in an argon atmosphere, has been examined. It has been shown that the substitution of the biladiene-type helicand by its 2,3- and especially 3,3′-analogues leads to a considerable enhancement of the chromophoric properties, an increase (up to 30-fold) of the fluorescence quantum yield, and an increase in the stability of corresponding dinuclear helicates [Zn2L2].

The high sensitive and selective "off-on" fluorescent Zn2+ sensor based on the Bis(2,4,7,8,9-pentamethyldipyrrolylmethene-3-yl)methane.

A fluorescent chemosensor based on the 3,3′-bis(dipyrrin) bearing two chromophoric dipyrrin units was synthesized, which showed a strongly enhanced fluorescent intensity in the presence of Zn2+ ions and a high selectivity toward Zn2+ ions over a wide range of tested metal ions in organic solvents.

meso-spacer influence on properties of zinc(II) complexes with 2,3′- and 3,3′-bis(dipyrrolylmethenes)

The study and comparative analysis of spectral-luminescent characteristics (absorption and fluorescence spectra), of quantum yield, and fluorescence life time in solutions, of lability in proton-donor media, solid phase thermal stability in air oxygen and argon was carried out for binuclear zinc(II) helicates with decamethyl-substituted 2,3′- and 3,3′-bis(dipyrrolylmethenes). The influence of molecular structure features of the ligands on the physicochemical properties of helicates was discussed.

Spectroscopic Studies of the Supramolecular Interactions Between Uracil and 5-Hydroxy-6-Methyluracil with Bovine Serum Albumin and its Bilirubin Complex

Using fluorescence and absorption spectroscopy the interaction of bovine serum albumin and its bilirubin complex with uracil and 5-hydroxy-6-methyluracil in phosphate buffer at pH 7.4 was investigated. The parameters of forming intermolecular complexes (binding constants, quenching rate constants, the radius of the quenching sphere and etc.) were determined. The interaction between serum albumin and uracils is carried out by the static quenching of protein fluorescence and has predominantly hydrophobic character. Using synchronous fluorescence spectroscopy the influence of uracil and 5-hydroxy-6-methyluracil on the conformational changes of the protein molecule was studied. Uracils effectively binds to bilirubin-albumin complex compared to free protein, which is caused by the interaction with tetrapyrrolic pigment in macromolecular complex. Molecular docking calculations also being presented.

Relationship between the spectral properties of solutions of borofluoride complex of alkylated dipyrromethene and the physicochemical parameters of solvents

Spectral and photophysical characteristics of borofluoride complex of alkylated dipyrromethene (Bodipy) are determined by means of absorption and fluorescence electron spectroscopy in various organic solvents. Dependences of the spectral and photophysical characteristics of Bodipy solutions vs. the physico-chemical parameters of solvents are obtained by linear regression analysis and the contribution from each parameter to the property under study is determined. It is established that the negative solvatochromic effect is intrinsic for Bodipy. It is concluded that specific interactions contribute substantially to the properties of the chromophore, which are determined by the electron donor properties of the solvent.