Benzoaza-15-crown-5 ethers: synthesis,structure, and complex formation with metal and ethylammonium ions

Benzoaza-15-crown-5 ethers containing one or two nitrogen atoms in different positions of the macrocycle and bearing different substituents at these atoms were synthesized. The structures of azacrown ethers and their metal complexes were studied by X-ray diffraction. The stability constants of the complexes of azacrown ethers with Na⁺, Ca²⁺, Ba²⁺, Ag⁺, Pb²⁺, and EtNH₃ ⁺ ions were determined by ¹H NMR titration in MeCN-d₃. In free benzoazacrown ethers containing secondary nitrogen atoms bound to the benzene ring, as well as in N-acetyl derivatives, the N atoms are sp²-hybridized and have a planar geometry. The nitrogen lone pairs on the p orbitals are efficiently conjugated to the benzene ring or the carbonyl fragment of the acetyl group, which is unfavorable for the complex formation. In addition, the formation of complexes with benzoazacrown ethers containing secondary nitrogen atoms is hindered because the hydrogen atoms of the NH groups are directed to the center of the macrocyclic cavity. In benzoazacrown ethers bearing N-alkyl substituents or secondary nitrogen atoms distant from the benzene ring, the N atoms show a substantial contribution of the sp³-hybridized state and have a pronounced pyramidal configuration, which promotes the complex formation. The lead and calcium cations form the most stable complexes due to the high affinity of Pb²⁺ ions for O,N-containing ligands, a high charge density on these ions, and the better correspondence of the cavity size of the 15-membered macrocycles to the diameter of the Ca²⁺ ion. An increase in the stability of the complexes is observed mainly in going from monoazacrown ethers to diazacrown ethers containing identical substituents at the N atoms and in the following series of substituents: C(O)Me < H < Me < CH₂CO₂Et. In the case of the CH₂CO₂Et substituents, the carbonyl oxygen atom is also involved in the coordination to the cation. The characteristic features of the complexing ability of N-alkylbenzomonoaza-15-crown-5 ethers bearing the nitrogen atom conjugated to the benzene ring show that macro-cyclic ligands having this structure are promising as selective and efficient complexing agents for metal cations.     

DFT calculation of benzoazacrown ethers and their complexes with calcium perchlorate

The complexation constants of several azacrown ethers with Ca(ClO₄)₂ were determined and turned out to be the higher, the large the macrocycle. The structures of free ligands and their complexes and the complexation energies were calculated by the DFT method. In the aza-12(15)-crown-4(5) ether complexes with Ca(ClO₄)₂, the metal cations lie outside the averaged plane of heteroatoms of the macrocycle, and the coordination of both counterions is V-like. In the complexes of aza-18-crown-6 ethers, the counterions are in the axial position relatively to the macrocycle in the center of which the Ca²⁺ ion is localized. The complexation energies increase with an increase in the size of the azacrown ether macrocycle. The involvement of the nitrogen atom in binding with the Ca²⁺ ion decreases with the expansion of the macrocycle. Two methods for quantitative estimation of the degree of pre-organization of ligands to complexation were considered: geometric and energetic methods. Benzoaza-15-crown-5 ether is a ligand which is more pre-organized to complexation than N-phenylaza-15-crown-5 ether.     

15-Hydroxybenzomonothia-15-crown-5 with the sulfur atom linked with the benzene ring and the derived sulfoxide: synthesis,structure, and complexation with the metal cations

Novel 15-hydroxybenzomonothia-15-crown-5 containing the sulfur atom linked with the benzene ring and its S-oxide were synthesized. The stability constants for the complexes of the obtained benzocrown ethers and a reference 15-hydroxybenzo-15-crown-5 with Na, Ca, Ag^I, Cd, Hg^II, and Pb^II perchlorates were determined by ¹H NMR titration. In MeCN-d₃, the benzothiacrown ether demonstrates a high selectivity towards the thio- and oxothiophilic Hg²⁺ (logK ₁ = 7.1) and Pb²⁺ ions (logK ₁ = 7.4). In MeCN-d₃-D₂O mixtures, the stabilities of the most of complexes decrease sharply due to competitive hydration of the metal cations except for the “soft” Ag⁺ and Hg²⁺ ions having low affinity for the “hard” oxygen atoms and, on the contrary, very high affinity for the “soft” S^II atoms. This results in the change in selectivity of complexation: at the water content in solution of 20%, the benzothiacrown ether binds preferably the Hg²⁺ (logK ₁ = 5.0) and Ag⁺ ions (logK ₁ = 2.7). In MeCN-d₃, the benzothiacrown-derived sulfoxide is a weak and non-selective complexing agent towards all the metal cations under study; the reference 15-hydroxybenzo-15-crown-5 forms more stable complexes with the oxophilic sodium, calcium, and lead(ii) cations. The conformational features of the benzocrown ethers and their metal complexes established by NMR spectroscopy and X-ray diffraction are discussed. The found characteristics of the complexing ability of benzomonothia-15-crown-5 where the sulfur atom is in conjugation with the benzene ring reveal that the macrocyclic ligands with such a structure are promising as high-selective and efficient complexing agents for the “soft” mercury(ii) and silver(i) cations in acetonitrile-water mixtures.     

Study of complexation of phenylaza-15-crwon-5, 4-nitrobenzo- 15-crown-5, and benzo-15-crown-5 with Ag+, Tl+ and Pb2+ ions in methanol by competitive potentiometry

The complexation reaction of phenylaza-15-crwon-5, 4- nitrobenzo- 15-crown-5, and benzo-15-crown-5 with Ag⁺, Tl⁺ and Pb²⁺ ions in methanol solution have been studied by a competitive potentiometric method. The Ag⁺/Ag electrode used both as an indicator and reference electrode in a concentration cell. The emf of cell monitored as the crown ethers concentration varies through the titration. The stoichiometry and stability constants of resulting complexes have been evaluated by MINIQUAD. The stoichiometry for all resulting complexes was 1:1. The stability of these metal ions with derivatives of 15-crown-5 are in order phenylaza-15-crown-5 > Benzo-15-crown-5 > 4-nitrobenzo-15-crown-5, and for the each used crown ethers are as Pb²⁺ > Ag⁺ > Tl⁺. The effect of the substituted group on the stability of resulting complexes was considered. The obtained results are novel and interesting.     

以2-苯氧乙基为氮支链的[18]和[15]环系氮支套索冠醚的合成及其络合性能

以2-苯氧乙醇为起始剂, 合成了两种新型氮支套索冠醚: N-(2-苯氧乙基)单氮杂-18-冠-6 (18CE)与N-(2-苯氧乙基)单氮杂-15-冠-5 (15CE). 通过红外光谱、核磁共振氢谱和紫外光谱表征了新冠醚及其中间体的结构. 用电导滴定法研究了两冠醚与Na^＋, K^＋, Ag^＋, NH^4＋, Ni^2＋, Cu^2＋, Pb^2＋和Co^2＋在25 ℃的配位作用, 计算了1∶1配合物的稳定常数. 实验结果表明, 由于N-(2-苯氧乙基)引入氮杂冠醚环和参与配位, 18CE和15CE配合物的稳定常数分别比单氮杂-18-冠-6, N-(2-羟基乙基)单氮杂-18-冠-6, N-(2-甲氧基乙基)单氮杂-18-冠-6和单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5的对应配合物明显提高. 配合物的稳定常数和紫外光谱皆提供了支链的苯氧基参与配位的信息.     

Synthesis and complexing properties of bis-crown ethers incorporating benzo-15-crown-5 and metallocene

Bis-crown ethers in which the benzo-15-crown-5 units were linked to 1,1′-positions of metallocene (M = Fe or Ru) with amide, ester, or ? C? C? bonds were synthesized. Complexing ability of the compounds with alkali, alkali earth, and transition metal cations were measured by the solvent extraction method. The results showed that these crown ethers had high affinity toward alkali metal cations (Li⁺, Na⁺, K⁺, and Rb⁺) and heavy-metal cations (Ag⁺ and Tl⁺). The difference of complexing ability for metal cations between ferrocene and ruthenocene derivatives could not be detected significantly. The extractability of metallocene-bis-crown ethers for metal cations was more larger than that of the corresponding mono-crown ethers, and irregular increments of extractability were explained by assuming the existence of a mixture of 1:1 and 2:1 complexes.     

Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali Cations

A series of double-armed benzo-15-crown-5 lariats (3–8) have been synthesized by the reaction of 4′, 5′-bis(bromomethyl)-benzo-15-crown-5 (2) with 4-hydroxybenzaldehyde, phenol, 4-chlorophenol, 4-methoxyphenol, 2-hydroxybenzaldehyde, and 4-acetamidophenol in 43 ~ 82% yields, respectively. The complex stability constants (K _S) and thermodynamic parameters for the stoichiometric 1:1 and/or 1:2 complexes of benzo-15-crown-5 1 and double-armed crown ethers 3–8 with alkali cations (Na⁺, K⁺, Rb⁺) have been determined in methanol–water (V/V=8:2) at 25 °C by means of microcalorimetric titrations. As compared with the parent benzo-15-crown-5 1, double-armed crown ethers 3–8 show unremarkable changes in the complex stability constants upon complexation with Na⁺, but present significantly enhanced binding ability toward cations larger than the crown cavity by the secondly sandwich complexation. Thermodynamically, the sandwich complexations of crown ethers 3-8 with cations are mostly enthalpy-driven processes accompanied with a moderate entropy loss. The binding ability and selectivity of cations by the double-armed crown ethers are discussed from the viewpoints of the electron density, additional binding site, softness, spatial arrangement, and especially the cooperative binding of two crown ether molecules toward one metal ion.     

Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali Cations

A series of double-armed benzo-15-crown-5 lariats (3–8) have been synthesized by the reaction of 4′, 5′-bis(bromomethyl)-benzo-15-crown-5 (2) with 4-hydroxybenzaldehyde, phenol, 4-chlorophenol, 4-methoxyphenol, 2-hydroxybenzaldehyde, and 4-acetamidophenol in 43 ~ 82% yields, respectively. The complex stability constants (K _S) and thermodynamic parameters for the stoichiometric 1:1 and/or 1:2 complexes of benzo-15-crown-5 1 and double-armed crown ethers 3–8 with alkali cations (Na⁺, K⁺, Rb⁺) have been determined in methanol–water (V/V=8:2) at 25 °C by means of microcalorimetric titrations. As compared with the parent benzo-15-crown-5 1, double-armed crown ethers 3–8 show unremarkable changes in the complex stability constants upon complexation with Na⁺, but present significantly enhanced binding ability toward cations larger than the crown cavity by the secondly sandwich complexation. Thermodynamically, the sandwich complexations of crown ethers 3-8 with cations are mostly enthalpy-driven processes accompanied with a moderate entropy loss. The binding ability and selectivity of cations by the double-armed crown ethers are discussed from the viewpoints of the electron density, additional binding site, softness, spatial arrangement, and especially the cooperative binding of two crown ether molecules toward one metal ion.Graphical Abstract Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali CationsYU LIU*, JIAN-RONG HAN, ZHONG-YU DUAN and HENG-YI ZHANG This revised version was published online in July 2005 with a corrected issue number.     

ELECTRON-TRANSFER REACTIONS OF CROSSLINKED POLY(1-PYRIDINIOMETHYL)STYRENE CHLORIDE 2. REDUCTION OF NITRO-COMPOUNDS

Continuing the study of electron transfer reactions of polypyridiniomethylstyrene chloride (PSPyCl), the reduction of nitro-compounds by the PSPyCl-Zn system was investigated. In general azoxy compounds were obtained as chief intermediate product of reduction. Reduction of nitrobenzo-15-crown-5 and its homologues give a new class of bis-crown ether compounds——azoxy-bisbenzocrown ethers. Azoxybisbenzocrown ethers undergo photoinduced trans-cis isomerization, which is reversible on irradiation with UV and on storage in darkness, similar to the case of azobiscrown ethers. Investigation of solvent extraction of various cations by azobiscrown ether isomers shows that cis-azoxybisbenzo-15-crown-5 exhibit good selectivity toward Nd~(3 ) from other rare earth cations.     

Synthesis and Complexing Properties of <Emphasis Type="Italic">N,N</Emphasis>′-Bis(2-hydroxyethyl) Diaza Crown Ethers

The stability constants of complexes of 12-, 15-, and 18-membered diaza crown ethers, N,N′-dimethyl diaza crown ethers, and N,N′-bis(2-hydroxyethyl) diaza crown ethers with alkali and alkaline-earth metal ions in 95% aqueous methanol at 25°C were determined. The stability of the complexes of unsubstituted diaza crown ethers with alkali metal cations is low, probably because of stabilization of the exo,exo conformation of the ligands due to interaction of the nitrogen lone electron pairs with the solvent. The complexes with the double-charged cations are appreciably more stable. N,N′-Dimethyl diaza crown ethers form stable complexes with all the ions studied. As compared to the dimethyl derivatives, N,N′-bis(2-hydroxyethyl) diaza crown ethers form more stable complexes with the Na⁺, K⁺, Ca²⁺, Sr²⁺, and Ba²⁺ ions, which is due to participation of the side hydroxyethyl groups in the coordination.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 665–669.Original Russian Text Copyright © 2005 by Kulygina, Vetrogon, Basok, Luk’yanenko.     

Synthesis,characterization, and photochemistry of the supramolecules formed from chromium(III) thiocyanato anion associated with crown ethers

A series of anionic chromium(III) thiocyanato complexes with metal crown ether cations have been prepared and characterized. These complexes have the form [Crown-M]₂⁺[Cr(NCS)₅(H₂O)]²⁻ and [Crown-M]₃⁺[Cr(NCS)₆]³⁻, where M=Na⁺, K⁺, or NH₄⁺ and crown represents the crown ether. The crown ethers are 15-crown-5, B-15-crown-5, 18-crown-6, DB-18-crown-6, and DB-24-crown-8, where B- and DB- stand for benzo- and dibenzo-, respectively. The complexes are stable for at least 20 h in the dark in dimethylformamide(DMF) or in acetonitrile, and they release thiocyanate slowly, k=(0.71–2.67)×10⁻⁹ mol/(L s) in acetonitrile in the dark. Photoanation of thiocyanate was observed for the complexes in DMF and in acetonitrile. The quantum yields of thiocyanate release in DMF and in acetonitrile are reported. The quantum yields were in the range 0.05 to 0.52 mol einstein⁻¹ and were solvent and wavelength dependent. In general, larger quantum yields were observed in DMF than in acetonitrile. The photoreaction mechanism is discussed.     

Synthesis,Biological Evaluation,and Molecular Modeling of Aza-Crown Ethers

Synthetic and natural ionophores have been developed to catalyze ion transport and have been shown to exhibit a variety of biological effects. We synthesized 24 aza- and diaza-crown ethers containing adamantyl, adamantylalkyl, aminomethylbenzoyl, and ε-aminocaproyl substituents and analyzed their biological effects in vitro. Ten of the compounds (8, 10–17, and 21) increased intracellular calcium ([Ca²⁺]_i) in human neutrophils, with the most potent being compound 15 (N,N’-bis[2-(1-adamantyl)acetyl]-4,10-diaza-15-crown-5), suggesting that these compounds could alter normal neutrophil [Ca²⁺]_i flux. Indeed, a number of these compounds (i.e., 8, 10–17, and 21) inhibited [Ca²⁺]_i flux in human neutrophils activated by N-formyl peptide (fMLF). Some of these compounds also inhibited chemotactic peptide-induced [Ca²⁺]_i flux in HL60 cells transfected with N-formyl peptide receptor 1 or 2 (FPR1 or FPR2). In addition, several of the active compounds inhibited neutrophil reactive oxygen species production induced by phorbol 12-myristate 13-acetate (PMA) and neutrophil chemotaxis toward fMLF, as both of these processes are highly dependent on regulated [Ca²⁺]_i flux. Quantum chemical calculations were performed on five structure-related diaza-crown ethers and their complexes with Ca²⁺, Na⁺, and K⁺ to obtain a set of molecular electronic properties and to correlate these properties with biological activity. According to density-functional theory (DFT) modeling, Ca²⁺ ions were more effectively bound by these compounds versus Na⁺ and K⁺. The DFT-optimized structures of the ligand-Ca²⁺ complexes and quantitative structure-activity relationship (QSAR) analysis showed that the carbonyl oxygen atoms of the N,N’-diacylated diaza-crown ethers participated in cation binding and could play an important role in Ca²⁺ transfer. Thus, our modeling experiments provide a molecular basis to explain at least part of the ionophore mechanism of biological action of aza-crown ethers.     

COMPETITIVE NMR STUDY OF THE COMPLEXATION OF SOME ALKALINE EARTH AND TRANSITION METAL IONS WITH 12-CROWN-4, 15-CROWN-5 AND BENZO-15-CROWN-5 IN ACETONITRILE SOLUTION USING THE LITHIUM-7 NUCLEUS AS A PROBE

Abstract

⁷Lithium NMR measurements were used to determine the stoichiometry and stability of Li⁺ complexes with 12-crown-4, 15-crown-5 and benzo-15-crown-5 in acetonitrile solution. A competitive ⁷Li NMR technique was also employed to probe the complexation of Mg²⁺, Ca²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Cd²⁺ ions with the same crown ethers. In all cases, the stability of the resulting 1:1 complexes was found to decrease in the order 15-crown-5 > benzo-15-crown-5 > 12-crown-4. Ca²⁺ and Cd²⁺ ions formed the most stable complexes in the series.     

Cation transport at 25°c from binary Na+Mn+, Cs+Mn+ and Sr2+Mn+ nitrate mixtures in a H2OCHCl3H2O liquid membrane system containing a series of macrocyclic carriers

Cation fluxes from binary mixtures of either Na⁺, Cs⁺ or Sr²⁺ with other alkali metal cations, alkaline earth metal cations, and Pb²⁺ through a H₂OCHCl³H₂O bulk liquid membrane system containing one of several macrocyclic carriers have been determined Nitrate salts were used in all cases. The most selective transport of Na⁺ over all other cations studied was found with the carrier cryptand [2.2.1]. Selective transport of Na⁺ relative to Li⁺, Cs⁺ and the alkaline earth cations was found with cryptand [2.2.2B] and cryptand [2.2.2D]. The ligands 21-crown-7 and dibenzo-24-crown-8 showed selective transport of Cs⁺ over the second cation in all cases. Several macrocycles showed selectivity for Sr²⁺ over the second cation with the macrocycle 1,10-diaza-18-crown-6 showing the highest selectivity for this cation of all ligands studied. Relative fluxes from binary cation mixtures are rationalized in terms of macrocycle cavity size, donor atom type and ring substituents.     

Separation of common monovalent and divalent cations by ion chromatography on calcined silica gel cation-exchange stationary phases, with tyramine-oxalic acid-containing crown ether mobile phases and indirect photometric detection

Summary Pure silica gels (Pia Seed 5S-60-SIL) calcined at 200, 400, 600, 800 and 1000°C for 5 h have been used as cation-exchange stationary phases in ion chromatography with indirect photometric detection for common monovalent and divalent cations (Li⁺, Na⁺, NH₄ ⁺, K⁺, Mg²⁺ and Ca²⁺); 0.75mm tyramine (4-(2-aminoethyl)phenol)-0.25mm oxalic acid, pH 5.0, containing crown ethers (18-crown-6 (1,4,7,10,13,15-hexaoxacyclooctadecane) or 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane)) was used as mobile phase. With increasing calcination temperature, the amounts of the crown ethers adsorbed on the calcined silica gel column increased and, consequently, the effect of the crown ethers as retention modifiers for these cations increased. Excellent simultaneous separation and highly sensitive detection of these cations at 275 nm were achieved in 17 min by use of a 150 mm×4.6 mm i.d. column packed with silica gel calcined at 1000°C and use of 0.75mm tyramine-0.25mm oxalic acid, pH 5.0, containing either 0.5mm 18-crown-6 or 5.0mm 15-crown-5 as mobile phase.     

Stability constants of complexes formed by new Schiff-base lariat ethers derived from 4,13-diaza-18-crown-6 with Ag+, Pb2+, Cu2+ cations determined by competitive potentiometry

The stability of complexes formed by a series of Schiff-base lariat ethers, derived from 4,13-diaza-18-crown-6, 1 with Ag⁺, Pb²⁺, Cu²⁺ cations, has been comparatively determined, in methanol: dichloromethane solution. We present here the synthesis and an interesting competitive potentiometry method useful for the stability constant determination for a new family of Schiff-base bibracchial lariat ethers. The stability constants and the selectivity in competitive complexation of Ag⁺, Pb²⁺ and Cu²⁺ cations by macrocyclic receptors 1–7 (L), can be accurately evaluated and species distribution diagrams can be calculated for individual system. In all cases further functionalization of bibracchial lariat ethers 2–7 is accompanied by an increasing of the selectivity, relative to the complexes of the initial 4,13-diaza-18-crown-6 macrocycle 1.     

p-tert-butylcalix[4]arenes containing azacrown ether substituents at the lower rim as potential polytopic receptors

A series of disubstituted p-tert-butylcalix[4]arenes with N-methoxycarbonylmonoazacrown ether and N-ethoxymonoazacrown ether residues at the lower rim has been prepared via the reaction of di(carboxymethoxy)-p-tert-butylcalix[4]arene with azacrown ethers and subsequent reduction of the resulting amide derivatives. Using UV titration and ¹H NMR spectroscopy we have demonstrated the ability of the calixarene with two N-carbonylmonoaza-18-crown-6-ether substituents to form the 1:3 complexes with K⁺ and Na⁺ and the 1:2 complexes with Cs⁺, Sr²⁺, Cu²⁺, and Zn²⁺. The calixarene with two fragments of N-ethoxymonoazo-18-crown ether has formed binuclear complexes with alkali metals cations and mononuclear complexes with transition metals cations.     

ESI-MS detection of very weak <Emphasis Type="Italic">π</Emphasis>-Stacking interactions in the mixed-ligand sandwich complexes formed by substituted benzo-crown ethers and metal cations

The stability of the mixed-ligand complex formed by amino-benzo-15-crown-5 and nitro-benzo-15-crown-5, with a metal cation, [NH₂B15C5+NO₂B15C5+K]⁺, was found to be enhanced by π-stacking interactions. This conclusion was deduced by comparison of the abundance of the mixed-ligand complex with the abundances of homo-ligand complexes ([(NH₂B15C5)₂+K]⁺, [(NO₂B15C5)₂+K]⁺), as well as with those of 1:1 complexes ([NH₂B15C5+K]⁺, [NO₂B15C5+K]⁺). Some solvents and some metal cations with large radii were also found to prevent the existence of π-stacking interactions.     

Cation-crown ether complex formation in water. II. Alkali and alkaline earth cations and 12-crown-4, 15-crown-5, and 18-crown-6

The stability constants and the partial molal volume and isentropic partial molal compressibility changes of complex formation between cations and crown ethers in water at 25°C are presented. The cations involved are Na⁺, K⁺, Rb⁺, Cs⁺, Ca²⁺, and Ba²⁺, and the crown ethers are 12-crown-4, 15-crown-5, and 18-crown-6. Values of V of complex formation have been discussed in terms of two simple models, one based on the scaled particle theory, and the others on the Drude-Nernst continuum model. The results indicate that the charge of the potassium cation in 18-crown-6 is especially well screened from the water. On this basis hydration numbers of complexed cations have been calculated. This shows that the size of the cation compared to the crown ether hole is important for the contacts between complexed cations and water.     

<Emphasis Type="Italic">N,N</Emphasis>’-Bis(acylvinylated) diaza-18-crown-6 ether as a lanthanide-selective macrocyclic complex-forming agent

Nucleophilic substitution in β-chlorovinyl phenyl ketone with diaza-18-crown-6 ether resulting in displacement of the chlorine atom afforded N,N’-bis(3-oxo-3-phenylpropen-1-yl)-1,10-diaza-18-crown-6 ether. The ability of the latter to form complexes with a number of metal cations was studied. However, the complex formation occurs only with the rare-earth cations Ln³⁺ and Th⁴⁺. This fact was demonstrated by UV and ¹H NMR spectroscopy of solutions, confirmed by isolations of glassy phases of composition L₃M₂(NO₃)₆ · nH₂O (M = La, Y, n ≈ 4–7), and supported by IR spectra of these phases in KBr pellets. The formation of complexes with La³⁺ and Y³⁺ leads to an increase in fluorescence intensity of the ligand. The stability constants of the 1 : 1 complexes in methanol were evaluated by spectrophotometry. These constants increase with decreasing ionic radius of the cation.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 156–160, January, 2005.