Konstantin Zhuravlev

Influence of ligand architecture on the structure of coordination centre in dimeric europium carboxylates with 1,10-phenanthroline

Abstract Methods of optical spectroscopy and X-ray crystallography data were used to examine the effect of architecture of carboxylate anions on structure of the Eu3+ coordination centre in europium carboxylates with 1,10-phenanthroline Eu(RCOO)3·Phen. Luminescence spectra of europium acetate, nitropropionate, benzoate, naphthylcarboxylates, phenylacetates, phenoxyacetate, triphenylpropionate were investigated. A few of europium carboxylates with 2,2′-bipyridine Eu(RCOO)3·Bpy and europium salts Eu(RCOO)3·nH2O were also studied. Vibrational IR and Raman spectra of phenylacetate family were analyzed. The crystal structure of nitropropionate Eu(NO2C2H4COO)3·Phen was solved by X-ray diffraction method. The predominant influence of steric hindrances on Eu3+ coordination centre was observed at increase of the size of aromatic fragment of carboxylate anions. It was demonstrated, that introduction of the methylene bridges between the carboxylic group and aromatic rings of ligand weakens the effect of steric factor.

Luminescence and structural properties of lanthanide complexes of Schiff bases derived from pyridoxal and amino acids

Lanthanide complexes of Schiff bases (SBs) with 1:1 and 1:2 (M:Lig) stoichiometric ratios were prepared by condensation of pyridoxal (PL) and aspartic acid (Asp) or l-histidine (His), respectively, in the presence of the appropriate metal chloride as a templating agent. These complexes were studied by optical spectroscopy and single crystal X-ray diffraction techniques. Crystallographic studies of 1:1 ([Eu(PL-Asp)(H(2)O)(4)](H(2)O)) and 1:2 ([Eu(PL-His)(2)(H(2)O)(2)]Cl(H(2)O)(4)) complexes show that Eu(III) is eight-coordinate in both structures, in a distorted square antiprism environment formed by the phenolic oxygen of PL, the nitrogen atom of carbon-nitrogen double bond, oxygen atoms of the carboxylate groups of His or Asp, and oxygen atoms of the water molecules. The main species formed in aqueous solutions containing these SBs have been determined by analysis of the luminescence spectra, lifetimes of Eu(III) excited states and vibronic interaction as well as structural features of the Eu(III) coordination sphere. Possible tetradentate coordination function of SBs in aqueous solutions with relatively high concentrations as well as the potential application of the lanthanide SB complexes as new luminescence materials are discussed.

INFRARED PHOTOLUMINESCENCE SPECTRA OF PBS NANOPARTICLES PREPARED BY LANGMUIR–BLODGETT AND LASER ABLATION METHODS

We optimized the optical setup originally designed for the photoluminescence measurements in the spectral range 400‒1100 nm. New design extends the spectral range into the near infrared region 900‒1700 nm and allows the colloidal solutions measurements in cuvettes as well as the measurements of nanoparticles deposited in the form of thin films on glass substrates. The infrared photoluminescence spectra of the PbS nanoparticles prepared by the Langmuir–Blodgett technique show the higher photoluminescence intensity and the shift to the shorter wavelengths compared to the infrared photoluminescence spectra of the PbS nanoparticles prepared by the laser ablation from PbS target. We aslo proved the high stability of PbS nanoparticles prepared in the form of thin layers.