Synthesis and characterization of new polymeric phthalocyanines substituted with diaza-18-crown-6 macrocycles through ethyleneoxy bridges

A tetranitrile monomer was synthesized by nucleophilic aromatic substitution of N,N′-bis(2-hydroxyethyl)-4,13-diaza-18-crown-6 onto 4-nitrophthalonitrile. A series of polymeric metal-free and metallophthalocyanine (M = 2H, Zn, Cu, Co and Ni) polymers was prepared by polymeric tetramerization reaction of the tetranitrile monomer with proper materials. The electrical conductivities of the polymeric phthalocyanines measured as gold sandwiches were found to be ∼10⁻⁹–10⁻⁴ S cm⁻¹ in a vacuum and in argon. The extraction ability of the metal-free polymeric phthalocyanine was evaluated in tetrahydrofuran using several alkali metal picrates such as Li⁺, Na⁺, K⁺ and Cs⁺. The extraction affinity of the metal-free polymeric phthalocyanine for K⁺ was found to be highest in the heterogeneous solid–liquid phase extraction experiments. The disaggregation property of the metal-free polymeric phthalocyanine was investigated with sodium, potassium and ammonium ions and methanol. All the novel compounds were characterized by using elemental analysis, UV–Vis, FT-IR, NMR and MS spectral data and DTA/TG.     

Complexation of silver(I) with different substituted diaza-18-crown-6 ethers in methanol

A large number of derivatives of the diaza-18-crown-6 ligand have been synthesized and characterized. These derivatives have different alkyl or aryl side arms at the nitrogen donor atoms of the macrocyclic diazacrown ether. In some side chains additional donor atoms are available. These diazacrown ethers are used as ligands for the complexation of Ag^I in MeOH. The complexation reactions have been studied using potentiometric and calorimetric methods. The thermodynamic data show the absence of a lariat effect. The increase of the values of the reaction enthalpies are due only to changes in solvation of the different ligands.     

Reduction of silver cation in the cavity of diaza-18-crown-6: A theoretical study

The structure and stability of diaza-18-crown-6 (1) complex with silver cation was studied by the density functional method with the PBE functional. The reduction of the cation in the macrocycle cavity was simulated and possible stability of the resulting van der Waals complex of the crown ether 1 with silver atom was analyzed. It is shown that, after electron capture, two equilibrium conformers of Ag⁺·1 give two structures locally stable with respect to the dissociation into the silver atom and the crown ether in its nearest equilibrium conformation. One of the neutral structures, that of the C _s symmetry, corresponds to a global minimum on the potential energy surface of the Ag⁰—1 system. It ensures the thermodynamic stability of the reduced complex with respect to dissociation. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 395–399, March, 2007.     

Interaction of uranyl monoaquadiformate with diaza-18-crown-6 in aqueous ethanol

The reaction of {[UO₂(HCOO)₂(H₂O)]} with diaza-18-crown-6 (DA18C6 = C₁₂H₂₆O₄N₂) in aqueous ethanol in the presence of formic acid yields the complexes {[DA18C6H₂]·[UO₂(HCOO)₃]₂} (I), [DA18C6H₂]·[UO₂(HCOO)₄] (II), and [DA18C6H₂]·(HCOO)₂·(H₂O)₂ (III). The complexes are characterized using IR spectroscopy, chemical analysis, and powder X-ray diffraction. From the comparison of the structural and spectral characteristics of [DA18C6H₂]·An₂·(H₂O)_2n (where An = Cl^?,NO ₃ ^? ,HCOO^?,HSO ₄ ^? ; n = 0.1), correlations are derived between the conformation of the [DA18C6H₂]²⁺ units and the conformation-sensitive frequencies. On the basis of these correlations, the conformations of the N⁺CCO and OCCO units were determined in the diazonia cations of compounds I and II and in [DA18C6H₂]·[UO₂(NO₃)₄]; the latter was prepared previously by reacting [UO₂(NO₃)₂(H₂O)₂]·(H₂O)₄ with DA18C6 in ethanol in the presence of nitric acid.     

Spectrophotometric study of interaction of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with diaza-18-crown-6 and diaza-15-crown-5 in acetonitrile and chloroform solutions

Interactions of diaza-18-crown-6 and diaza-15-crown-5, as electron donors, with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), as an electron acceptor, have been investigated spectrophotometrically in acetonitrile and chloroform solutions. The results indicated immediate formation of an electron donor-electron acceptor complex DA: [reaction in text] which is followed by two relatively slow consecutive reactions: [reaction in text]. The pseudo-first-order rate constants for the formation of the ionic intermediate and the final product have been evaluated at various temperatures by computer fitting of the absorbance time data to appropriate equations. The formation constants of the resulting DA complexes have also been determined. The influences of both the azacrown's structure and the solvent properties on the formation of DA complexes and the rates of subsequent reactions are discussed.     

Macroheterocycles. 24. Synthesis of new derivatives of diaza-18-crown-6

New derivatives of diaza-18-crown-6 have been prepared by the aminomethylation of N-alkylsulfonamides under the action of N,N-bismethoxymethyldiaza-18-crown-6.For Communication 23, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 413–415, March 1986.     

New quaternary ammonium salts and metal complexes of organylheteroacetic acids with diaza-18-crown-6 ether

Quaternary ammonium salts 2(RCH₂COO)⁻·(2H·DACE)⁺ were synthesized in up to 98% yield by the reaction of biologically active organylheteroacetic acids (OHA) RCH₂COOH with diaza-18-crown-6 ether (DACE).     

A thermodynamic study of the association of alkali metal cations with dicyclohexano-18-crown-6

A thermodynamic study of the association of Na⁺, K⁺, Rb⁺, and Cs⁺ with dicyclohexano-18-crown-6 in acetonitrile has been carried out at 308, 303, 298, 293, and 288 K using a conductometric technique. The observed molar conductivities, A, were found to decrease significantly for mole ratios less than unity. A model involving 11 stoichiometry has been used to analyze the conductivity data. The stability constant,K, and the limiting molar conductivity, A _c , for each 11 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of logK at 298 K, as derived from this study is K⁺>Na⁺>Rb⁺>Cs⁺. Values of H ^o and S ^o are reported and their significance is discussed.     

含二氮杂-18-冠-6-单元的向列型液晶化合物的合成和性质

本文报道三种含芳酯的二氮杂-18-冠-6的合成。它们显示出向列型液晶的特性。探讨了分子结构对液晶性质的影响。冠醚液晶7在无机盐掺杂后是否仍有液晶性质与掺杂的无机盐阴离子的结构有关, 而与阳离子的种类无关。无机盐掺杂量对液晶清亮的影响也作了研究。     

Synthesis and complexation properties of photochromic benzochromenes containing aza-and diaza-18-crown-6-ether fragments

Complex formation of Mg²⁺, Ba²⁺, and Pb²⁺ perchlorates with 3,3-diphenyl-3H-benzo[f]chromenes containing aza-and diaza-18-crown-6-ether or morpholine fragments was studied. The strong influence of the metal cations on the spectral characteristics of these organic ligands and on the kinetic of photochromic transformations was found. The results obtained were explained by the formation of carbonyl-“ capped” complexes of various structures. Faculte des Sciences de Luminy, Universite de la Mediterranee, UMR 6114 CNRS, 13288 Marseille, France. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 280—287, February, 2006.     

Study of complex formation between 18-crown-6 and diaza-18-crown-6 with uranyl cation (UO2 2+) in some binary mixed aqueous and non-aqueous solvents

The complexation reaction between UO₂ ²⁺ cation with macrocyclic ligand, 18-crown-6 (18C6), was studied in acetonitrile–methanol (AN–MeOH), nitromethane–methanol (NM–MeOH) and propylencarbonate–ethanol (PC–EtOH) binary mixed systems at 25 °C. In addition, the complexation process between UO₂ ²⁺ cation with diaza-18-crown-6 (DA18C6) was studied in acetonitrile–methanol (AN–MeOH), acetonitrile–ethanol (AN–EtOH), acetonitrile–ethylacetate (AN–EtOAc), methanol–water (MeOH–H₂O), ethanol–water (EtOH–H₂O), acetonitrile–water (AN–H₂O), dimethylformamide–methanol (DMF–MeOH), dimethylformamide–ethanol (DMF–EtOH), and dimethylformamide–ethylacetate (DMF–EtOAc) binary solutions at 25 °C using the conductometric method. The conductance data show that the stoichiometry of the complexes formed between (18C6) and (DA18C6) with UO₂ ²⁺ cation in most cases is 1:1 [M:L], but in some solvent 1:2 [M:L₂] complex is formed in solutions. The values of stability constants (log K_f) of (18C6 · UO₂ ²⁺) and (DA18C6 · UO₂ ²⁺) complexes which were obtained from conductometric data, show that the nature and also the composition of the solvent systems are important factors that are effective on the stability and even the stoichiometry of the complexes formed in solutions. In all cases, a non-linear relationship is observed for the changes of stability constants (log K_f) of the (18C6 · UO₂ ²⁺) and (DA18C6 · UO₂ ²⁺) complexes versus the composition of the binary mixed solvents. The stability order of (18C6 · UO₂ ²⁺) complex in pure studied solvents was found to be: EtOH > AN ≈ NM > PC ≈ MeOH, but in the case of (DA18C6 · UO₂ ²⁺) complex it was : H₂O > MeOH > EtOH.     

Fluorescence and NMR binding studies of N-aryl-N'-(9-methylanthryl)diaza-18-crown-6 derivatives

N-Aryl-N'-(9-methylanthryl)diaza-18-crown-6 derivatives perform as fluorescent photoinduced electron-transfer (PET) sensors with very selective response toward Ca(2+) versus Mg(2+), Na(+), and K(+). The fluorescence intensity was increased by a factor of up to 170 in the presence of Ca(ClO(4))(2). (1)H NMR studies show that metal cations affect these molecules very differently: Ca(2+) has a global effect on each molecule, while Mg(2+) affects part of each molecule, and K(+) and Na(+) affect each molecule moderately, which is very consistent with the fluorescence response.     

Crystal Structure of N,N'-Bis(dodecyl)diaza- 18-crown-6 Complexed Sodium Perchlorate

The crystal structure of a new complex of a diaza-crown ether having two side arms has been determined from X-ray diffraction data. The compound crystallizes in space group P1 with cell dimensions a = 9.982(1), b = 10.685(1), c = 20.376(2)Å, = 81.09(1), = 80.92(1), = 88.43(1)0, Z = 2. The structure has been solved by direct methods and refined to the final R value of 0.053 for 3458 observed reflections and 424 parameters. The diaza-18-crown-6 ligand adopts an approximate D3d conformation. The Na+ ion is held inside the molecular cavity of this macroring ligand and a ClO-4 oxygen coordinates with Na+. The average Na–-O (18-crown-6) and Na–-N bond lengths are 2.426(4) and 2.786(5)Å, respectively; the Na–-O (ClO-4) bond length is 2.472(4)Å. The mean cavity radius is 1.10 Å and the NN nonbonding distance is 4.605(6)Å.     

Photonics of 18-crown-6-containing styryl dye and its complexes with metal cations

Using absorption, luminescence, ¹H NMR, and laser kinetic spectroscopies, the photophysical processes and photochemical reactions of 4-[(E)-2-(2,3,5,6,8,9,11,12,14,15-decahydro-1,4,7,10,13,16-benzohexaoxacyclooctadecin-18-yl)vinyl]-1-ethylpyridinium perchlorate and its complexes with lithium, sodium, potassium, calcium, barium, silver, and lead perchlorates in MeCN have been studied. The styryl dye and its complexes with metal cations are capable of emitting normal (prompt) and delayed fluorescence and enter into the trans–cis photoisomerization reaction. The dye molecules in the triplet state participate in the processes of degradation of electronic excitation energy. Triplet–triplet absorption is observed only in the presence of lead cations with a maximum at 470 nm and the deactivation rate constant of the triplet state k = 2.5 × 10⁴ s^–1 in a deoxygenated solution.