ABSTRACT
The aim of this work is to apply organic-inorganic hybrid salts made of imidazo[1,5-a]pyridinium-based cations and halometallate anions as fluorescent agents to modify cross-linked polyurethane (CPU) for the creation of flexible photoluminescent films. The use of ionic compounds ensures excellent dispersion of the luminescent components in the polymer matrix and prevents solid-state quenching. The absence of phase segregation makes it possible to fabricate uniformly luminescent films with a large area. To this, new tetrachlorocadmate salts [L]2[CdCl4] (1) and [L']2[CdCl4] (2), where L+ is 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium and [L']+ is 2-methylimidazo[1,5-a]pyridinium cations, have been prepared and characterized by IR, NMR, UV-Vis spectroscopy and single crystal X-ray diffraction. The organic cations resulted from the oxidative cyclization-condensation involving CH3NH2·HCl and 2-pyridinecarbaldehyde in methanol (1), and formaldehyde, CH3NH2·HCl and 2-pyridinecarbaldehyde in an aqueous media (2). In the crystal of 1, loosely packed tetrahedral cations and π-π stacked anions are arranged in separate columns parallel to the a-axis. The pseudo-layered structure of 2 is built of the organic and inorganic layers alternating along the a axis. The adjacent CdCl4 2- anions in the inorganic layer show no connectivity. The organic-inorganic hybrids 1 and 2 were immobilized in situ in the cross-linked polyurethane in low content (1 wt%). The photoluminescent properties of 1 and 2 in the solid state and in the polymer films were investigated. The semi-transparent CPU films, that remain stable for months, retain the photoluminescent ability of both hybrids in the blue region with a prominent red shift in their emission.
ABSTRACT
In this study, we report soft and solvothermal methods for synthesis of zinc oxide nanoparticles (ZnO NPs). Both methods involve a precursor and are carried out at the middle low-temperature regime. The effect of different solvents on the ZnO NPs properties was studied. The nonlinear optical (NLO) response of the NPs was analyzed by the self-action of picosecond laser pulses at 1064 nm and by second harmonic generation (SHG) of a femtosecond laser pulses pump at 800 nm. The luminescence was studied within UV-visible ranges. It was shown that the NLO response efficiency significantly depends on the solvent. The obtained SHG efficiency of small (~2 nm) ZnO NPs is comparable to the one obtained for large (~150 nm) commercial ZnO NPs. The observed results are important for the application of the ZnO NPs in biolabeling.
ABSTRACT
Two novel compounds, the organic-inorganic hybrid [L](2)[ZnCl(4)] (1) and the coordination complex LZnCl(3) (2), where L is the 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium cation, were prepared using the oxidative condensation-cyclization of 2-pyridinecarbaldehyde and CH(3)NH(2)·HCl in methanol in the presence of Zn(2+) cations. The metal-free interaction of the organic components afforded the salt [L][Cl]·1.5H(2)O (3). The use of methylamine hydrochloride instead of its aqueous solution is believed to be responsible for the cyclocondensation with the formation of L instead of the expected Schiff base ligand. Compounds 1-3 have been obtained as single crystals and characterized by elemental analysis, IR, NMR spectroscopy, and single-crystal X-ray diffraction techniques. The structure of 1 is described as layers of cations and anions stacked along the c-axis, with the minimum ZnZn distance being 8.435 Å inside a layer. In the crystal lattice of 3, the cations are arranged in stacks propagating along the a-axis; the 1D H-bonding polymer built of chloride ions and water molecules runs parallel to a column of stacked cations. The organic cations in salts 1 and 3 show various patterns of π-π stacking. The discrete molecular structure of 2 shows coordination of a Zn atom to the N(pyridyl) atom, which enables one of the chloride atoms attached to the metal centre to interact with a π-system of the positively charged imidazolium ring. Numerous C-HCl contacts in a 1-3 are seen as space-filling van der Waals interactions of minor importance in determining crystal packing. The (1)H NMR studies suggest that the Zn-N coordination found in the solid-state structure of 2 is not retained in dmso, and 1, 2 and 3 are completely dissociated in solution. The emission spectra of 1 and 2 (λ(max) = 455 and 445 nm, respectively) exhibit red-shifts of fluorescence wavelength when compared to 3 and differ in the shapes and maxima of the emission as well as in relative fluorescence intensity.
ABSTRACT
A solid-phase reagent based on 1-(4-adamantyl-2-thiasolylazo)-2-naphthol adsorbed onto silica gel was prepared for Co(II) recovery and preconcentration prior to its sorption-spectroscopic detection. The immobilized reagent was applied to the determination of free cobalt ions in natural water. The solid-phase reagent and chemiluminescent method coupled with membrane filtration, gel-permeation and ion-exchange chromatography were applied to the study of the speciation of iron and cobalt in water from the Dnieper reservoirs and lakes of Kyiv City; their predominant forms were complexes of Fe(III) and Co(II) with dissolved organic matter and fulvic acids play a main role in their complexation.