A dual-emissive ytterbium complex with a pyrene-substituted Schiff base ligand was synthesized and characterized. The complex exhibits both visible and near-infrared (NIR) emissions, with the emission bands ratio showing a significant temperature dependence in the range of 77-420 K. This feature makes the complex suitable for luminescent thermometry applications including inside of the organic light-emitting diode (OLEDs) emission layer (EML). Several heterostructures with different hole transport layers and different thicknesses of the EML were tested. The OLED1 with thinner EML demonstrate external current efficiency (ECE) up to 30 mu W/W while electroluminescence spectra contain both vis and NIR emission bands that make it possible to measure EML temperature which reach up to 77-114 degrees C.

A series of microcrystalline NaYF4 nanoparticles doped with Yb and Er were synthesized, and their Stokes and anti-Stokes emission was studied. Its temperature dependence made it possible to obtain high-temperature luminescent thermometry materials. The prospects of both Stokes and anti-Stokes luminescence for luminescent thermometry were studied and discussed.

ratiometric luminescent thermometers, particularly lanthanide-based, become very important, and long wavelength range is of particular interest due to low signal scattering. With this in mind, a series of new red and NIR emitting lanthanide Schiff base complexes were synthesized and characterized in detail for use as components of luminescent thermometers. Red-emitting europium complexes demonstrated high temperature sensitivity (up to 7 %/K) in the cryogenic temperature range (80-200 K), where the ligand-to-europium luminescence intensity ratio (LIR) was used as a signal. In contrast, NIR emitting ytterbium complexes demonstrated no sensitivity in the cryogenic range; however, their luminescence was sensitive to high temperatures (300-600 K), which is currently of particular interest. Ytterbium and europium complexes were also tested in OLEDs, and due to high temperature sensitivity, europium complexes were used for the first electroluminescent thermometers.

Heterobimetallic lanthanide conjugates were obtained by click-reaction between two monometallic lanthanide complexes with Schiff bases for the first time. For that, novel azido- and ethynyl-substituted ligands, as well as their lanthanide complexes, were obtained and characterised; two new crystal structures were obtained. Click-reaction between ligands and complexes was performed, and the latter was demonstrated to result in the conjugates {Ln1-Ln2} formation. Among the obtained conjugates, {Yb-Nd} and {Yb-Er} demonstrated intense NIR emission with temperature sensitivity in the physiological range of up to 3%/K.

Management of high-level waste is essential for the further sustainable development of nuclear energy. Solvent extraction is one of the technologically acceptable methods for carrying out such processing. The search for new selective extractants is an urgent task that requires systematic research into the structure-properties relationship. 1,10-phenanthroline-2,9-diamides (DAPhen) is a promising ligand class for processing such solutions. Identification of the binding and separation mechanism is the most important fundamental question for any separation system. In this work, we systematically studied of the mechanism of extraction and complex formation by this class of compounds on the example of 4,7-substituted aliphatic 1,10-phenanthroline-2,9-diamides. For systematic comparison, we conducted liquid-liquid extraction studies of f-elements and nitric acid, determination of binding constants (UV–vis and luminescence titration), and structural studies of complexes. Using these methods, it was shown how electron-withdrawing substituents (-Cl) and electron-donating (-OBu) significantly affect the Brønsted and Lewis basicity, the stoichiometry of the complexes formed and the trends in the extraction of f-elements. Moreover, XRD study of an array of complex compounds allowed us to establish the structural features that determine the efficiency and selectivity of liquid-liquid extraction.

Samples of crystalline cubic phased ceramics based on (Zr1-& khcy;Hf & khcy;)(0.82)Y0.17Eu0.01O1.91 with different contents of hafnium (& khcy; = 0; 0.21; 0.50; 0.77; 1) were synthesized. The synthesis conditions were chosen to avoid the possible formation of a minor tetragonal phase. The average grain size was 2-5 microns. The structural parameters of ceramics, their band gap, luminescent and thermoluminescent properties were studied depending on the hafnium content. It was shown that single-phase sample with calculated formula ((Zr0.77Hf0.23)(0.82)Y0.17Eu0.1)O-1.91 demonstrated the highest cathodoluminescent intensity upon excitation by electrons. It was found that thermoluminescent properties of ceramics with hafnium content of & khcy; = 0.50-0.77 range are prospective for application in thermodosimetry. The highest luminescence yield was observed in such samples.

Fourier transform infrared spectroscopy (FT-IR) is a widely used spectroscopic method for routine analysis of substances and compounds. Spectral interpretation of spectra is a labor-intensive process that provides important information about functional groups or bonds present in compounds and complex substances. In this paper, based on deep learning methods of convolutional neural networks, models were developed to determine the presence of 17 classes of functional groups or 72 classes of coupling oscillations in the FT-IR spectra. Using web scanning, the spectra of 14 361 FT-IR spectra of organic molecules were obtained. Several different variants of model architectures with different sizes of feature maps have been tested. Based on the Shapley additive explanations (SHAP) and gradient-weighted class activation mapping (GradCAM) methods, visualization tools have been developed for visualizing and highlighting the areas of absorption bands manifestation for corresponding functional groups or bonds in the spectrum. To determine 17 and 72 classes, the F1-weighted metric, which is the harmonic mean of the class' precision and class' recall weighted by class' fraction, reached 93 and 88%, respectively, when using data on the position of absorption maxima in the spectrum as an additional source layer. The resulting model can be used to facilitate the routine analysis of spectra for all areas such as organic chemistry, materials science, and biology, as well as to facilitate the preparation of the obtained experimental data for publication.

Four new NIR-emitting ytterbium complexes Ln(L)(HL) and K[Ln(L)2](H2O)n (Ln = Yb, Lu; L = 2-tosylaminobenzaldehyde-4-azidomethylbenzoylhydrazone (L1) and 2-tosylamino-5-bromobenzaldehyde-4-azidomethylbenzoylhydrazone (L2)) were obtained and characterized, and 6 crystal structures of Yb(L1)(HL1), Lu(L2)(HL2), Lu (L2)(HL2)(n-Hex) (n-Hex =n-Hexane), K[Lu(L1)2](H2O), {KYb(L1)2(H2O)2(THF)}2 and K[Yb(L2)2](THF) were determined. Rational design yielded complexes with intense NIR emission, a Stokes shift of 500 nm (16 100 cm-1), and sensitivity towards the S2-anion. The complexes could penetrate cells, and showed low toxicity.

A novel polydentate chelating antioxidant ligand and series of organotin complexes on its base were synthesized and characterized by NMR 1H, 13C, 119Sn, IR spectroscopy, X-ray, and elemental analysis. Their antioxidant activity was evaluated in DPPH and NBT-tests, and as lipoxygenase inhibitory activity. It was shown that ligand alone is a radical scavenger, while introducing tin in the structure of the compound significantly decreases its activity. For the ligand alone the ability to strongly suppress the formation of advanced glycation end products (AGEs) was shown, which may be associated with the established antiradical activity. All synthesized compounds appeared to be moderate lipoxygenase inhibitors. The stability of compounds to hydrolysis under different pH was estimated. The ligand undergoes decomposition after about an hour, while organotin complexes on its base demonstrate vast stability, showing signs of decomposition only after 5 h of experimentation. Cytotoxicity of compounds was studied by standard MTT-test, which showed unorthodox results: the ligand itself demonstrated noticeable cytotoxicity while the introduction of organotin moiety either did not affect the toxicity levels or reduced them instead of increasing. Organotin complexes possess luminescence both as powders and DMSO solutions, its quantum yields reaching 67% in DMSO. The combination of luminescence with unique cytotoxic properties allows us to propose the synthesized compounds as perspective theranostic agents.

New ytterbium complexes K(Solv)x[Yb(Ln)2] (Solv = ethanol and/or water) with 2-tosylaminobenzylidene-aryloylhydrazones (H2L1, aryloyl = benzoyl; H2L2, aryloyl = 2-naphthoyl) demonstrated high solubility and hole mobility (ca. 2.6 × 10-6 cm2 V-1 s-1), while their electron mobility and PLQY were different. The substitution of a benzoyl substituent with naphthoyl resulted in a significant increase of the electron mobility (6.9 × 10-7vs. 1.7 × 10-6 cm2 V-1 s-1) and a decrease of the quantum yield (1.2% vs. 0.6%). As a result, the optimized OLEDs based on the K[Yb(Ln)2] layer demonstrated efficiencies up to 385 μW W-1 and 441 μW W-1, indicating the superior importance of charge mobility over the quantum yield. These are the highest efficiencies of the Yb electroluminescence.

An approach to the directed synthesis of aromatic lanthanide carboxylates as promising candidates for various luminescent applications, first of all, as emitting layers in light-emitting diodes, by varying the conjugation length with the introduction of a heteroatom and a neutral ligand was proposed. This approach enabled the synthesis of new europium and ytterbium complexes with naphtho[1,2]thiazole-2-carboxylic and naphtho[2,1]thiazole-2-carboxylic acid anions, which were successfully used in light-emitting diodes.

The well-known system of dinuclear Cu(I) complexes bridged by 2-(diphenylphosphino)pyridine (PyrPhos) derivatives Cu2X2L3 and Cu2X2LP2 (L = bridging ligand, P = ancillary ligand) goes along with endless variation options for tunability. In this work, the influence of substituents and modifications on the phosphine moiety of the NP-bridging ligand was investigated. In previous studies, the location of the lowest unoccupied molecular orbital (LUMO) of the copper complexes of the PyrPhos family was found to be located on the NP-bridging ligand and enabled color tuning in the whole visible spectrum. A multitude of dinuclear Cu(I) complexes based on the triple methylated 2-(bis(4-methylphenyl)phosphino)-4-methylpyridine (Cu-1b-H, Cu-1b-MeO, and Cu-1b-F) up to complexes bearing 2-(bis(4-fluorophenyl)phosphino)pyridine (Cu-6a-H) with electron-withdrawing fluorine atoms over many other variations on the NP-bridging ligands were synthesized. Almost all copper complexes were confirmed via single crystal X-ray diffraction analysis. Besides theoretical TDDFT-studies of the electronic properties and photophysical measurements, the majority of the phosphino-modified Cu(I) complexes was tested in solution-processed organic light-emitting diodes (OLEDs) with different heterostructure variations. The best results of the OLED devices were obtained with copper emitter Cu-1b-H in a stack architecture of ITO/PEDOT-PSS (50 nm)/poly-TPD (15 nm)/20 wt % Cu(I) emitter:CBP:TcTA(7:3) (45 nm)/TPBi (30 nm)/LiF(1 nm)/Al (>100 nm) with a high brightness of 5900 Cd/m2 and a good current efficiency of 3.79 Cd/A.

Ytterbium complexes Yb(LX)(HLX) with 2-tosylamino-4-bromobenzylidene-X-benzoylhydrazones (H2LH, X = H; H2LF, X = F; H2LI, X = I) were obtained, their luminescent properties characterized. Halogenation resulted in the increase of solubility (up to 24 g/L in THF) and quantum yield (up to 1.9%). High solubility and high quantum yields resulted in successfully testing these complexes as purely NIR-emitting host-free emitting layers in OLEDs. Surprisingly, among the tested materials the highest efficiency (110 mu W/W) was demonstrated by the Yb(LH) (HLH) complex with the lowest quantum yield (0.5%). This efficiency is the highest for the Yb electroluminescence by far, and it was obtained for the solution-processed OLED.

The approach to the directed synthesis of lanthanide aromatic carboxylates – precursors to the electroluminescent materials, - was proposed, namely the conjugation length increase and heteroatom introduction in the appropriate position in combination with the neutral ligand introduction. This resulted in the isolation of a series of new lanthanide complexes, among which the highest electroluminescence efficiency was obtained for mixed-ligand europium benzothiazole-2-carboxylate with bathophenanthroline in a solution-processed OLED. The peculiarities of energy transfer processes allowed obtaining luminescence thermometer materials based on this system, which demontrated the sensitivity of 2.8%/K in the physiological range.

The principles of the “multiphotonic emission”, i.e. multiple emission from one lanthanide ion, in heterometallic lanthanide terephthalates were determined. Thanks to it, another system with the same effect, namely EuxY1-x(dbm)3(Phen) (Hdbm – dibenzoylmethanate, Phen – o-phenanthroline (mistape)) was found. The criteria for concentration quenching appearance were formulated and demonstrated.

Europium 2-benzofuranoate Eu(BFC)3(H2O)3 was successfully used for bioimaging in cellulo due to the combination of high solubility and high luminescence intensity in solution. It was possible due to the purposeful variation of the aromatic core of carboxylate anion.