Lada N. Puntus

Influence of non-covalent interactions on properties of lanthanide systems with aromatic ligands

Abstract Two series of lanthanide compounds, namely, chlorides containing different numbers of both 1,10-phenanthroline (Phen) molecules and chloride anions in the first coordination sphere, and Schiff Bases (SBs) derived from Pyridoxal (PL) and amino acids, were characterized by single crystal X-ray diffraction and luminescence techniques. The combined use of these techniques for the analysis of long-distance europium non-covalent interactions was performed for the first time. As a result, the correlation between supramolecular organization and the features of the Eu III electronic transitions was found for the compounds of the first series. Strong non-covalent interactions between pyridoxal rings of SBs (the second series of compound) led to the formation of 1:2 species and four-dentate coordination function of these SBs in aqueous solution.

Polyphenylenepyridyl dendrimers as stabilizing and controlling agents for CdS nanoparticle formation

Semiconductor nanoparticles (NPs) are being actively explored for applications in medical diagnostics and therapy and numerous electronic devices including solar cells. In this paper we demonstrate the influence of the third generation rigid polyphenylenepyridyl dendrimers (PPPDs) of a different architecture on the formation of well-defined CdS NPs. A high temperature approach to the synthesis of novel CdS/PPPD nanocomposites is feasible due to the high thermal stability of PPPDs. The PPPD architecture affects the CdS NP formation: larger NPs are obtained in the presence of dendrimers with 1,3,5-triphenylbenzene cores compared to those with tetrakis(4-ethynylphen-1-yl)methane cores. The reaction conditions such as concentrations of PPPDs and NP precursors and the temperature regime also influence the CdS NP sizes. For the first time, we elucidated a mechanism of CdS NP formation in a non-coordinating solvent through the CdO redispersion in the presence of PPPDs. Interesting optical properties of these CdS/PPPD nanocomposites make them promising candidates for imaging applications.

The Dark Side of Hydrogen Bonds in the Design of Optical Materials: A Charge‐Density Perspective

A combined investigation of the structural, electronic, and optical properties of three crystalline nonaaqualanthanoid(III) triflates, [Ln(H2 O)9 (CF3 SO3 )3 ], has provided unambiguous experimental evidence for charge redistribution in the first coordination sphere of a lanthanide ion as a result of hydrogen bonds with outer-sphere anions. As well as resulting in charge transfer from the noncoordinated anions to the coordinated water molecules, these hydrogen bonds give rise to a new excited state, an hydrogen-bond-induced charge-transfer state, which is observed experimentally for the first time. This state was shown to be responsible for the previously unknown negative aspect of hydrogen bonds with a lanthanide-bound water molecule: rather than increasing the luminescence efficiency of the complex, they can lead to additional quenching that is unfavorable for the task-specific design of optical materials.

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.

An efficient route for design of luminescent composite materials based on polyethylene containing europium dibenzoylmethanate

Luminescent composite materials based on linear polyethylene doped by a well dispersed tetrakis dibenzoylmethanate europium complex have been developed. The anion of the latter serves as an efficient light harvesting antenna and possesses the desired photophysical properties. The targeted modification of the Eu complex, namely introduction of a long hydrocarbon chain into the tetraalkylammonium cation [RNEt3]+, has ensured the compatibility of the complex with the polyethylene matrix. The [RNEt3]+ cation has been obtained by using long-chained 1-iodoalkanes synthesized via the Nd-catalyzed ethylene oligomerization process. The photophysical properties and the homogeneity of the obtained composites have been controlled by optical spectroscopy, luminescence intensity mapping as well as scanning electron microscopy.

Luminescent lanthanide complexes for advanced photonic applications

The lanthanide compounds containing unsymmetrical β-diketone with [2.2]paracyclophane moiety in particular the europium complex with three [1-(4-[2.2]paracyclophanyl)]-3-phenylpropane-1,3-dione and 1,10-phenanthroline has been synthesized for the first time. The optical properties of [2.2]paracyclophane-derived ligands (symmetrical β-diketones and their respective N-phenylimines) as well as those of the europium complex were studied by UV-visible and luminescence spectroscopy. The diastereomers (racemic chiral, (R*,R*)- and achiral meso, (R,S)-) of the β-diketones and their respective N-phenylimines exhibit quite identical absorption spectra with intense broad band centered at 360 and 380 nm, respectively. The designed blue-emitting unsymmetrical β-diketone acts as a very efficient sensitizer of the EuIII emission and does so in the near-UV region. The introduction of [2.2]paracyclophane moiety in the β-diketones allows to expand the excitation wavelength of the lanthanide complex up to 500 nm and to obtain the relatively high overall quantum yield for the europium ion.

The correlation between SHG efficiency and structural peculiarities of [2.2]paracyclophane derivatives

ABSTRACT Nonlinear optical properties of 24 derivatives of [2.2]paracyclophane (pCp) have been analyzed. The set of the compounds studied include such classes as β-diketones, formyl-metoxy and formyl-hydroxy derivatives of pCp, pCp-Cr(CO)3, imines including Schiff bases. All molecules studied exhibit second harmonic generation ability, the efficiency of which was measured by the powder technique. In order to elucidate the role of intramolecular charge transfer due to transannular interaction in pCp the DFT calculations of the number of benzene analogues have been performed as well. For the first time the diastereomeric approach for the design of NLO materials was proposed and successfully utilized.

Linear and nonlinear optical properties of new materials based on DNA-CTMA and aromatic compounds (Conference Presentation)

In order to find eco-friendly materials for different applications an important research effort was devoted to the materials science in the last decade. A particular attention attracted the deoxyribonucleic acid (DNA). The interest is due to its versatility, biodegradability, abundance and their origin from renewable sources. DNA based new materials, functionalized with hexadecyltrimethylammonium chloride (CTMA) and aromatic compounds were prepared. Solutions with two different concentrations of aromatic compounds were obtained in butanol. The obtained, new complexes were processed into good optical quality thin films by spin coating method. Films were deposited on glass substrates and characterized for their spectroscopic, linear and nonlinear optical properties. The third-order nonlinear optical (NLO) properties of thin films were determined by the optical third-harmonic generation technique at 1 064.2 nm fundamental wavelength. The obtained materials, with improved fluorescence efficiency, present a potential interest for application in photonics.