Inductive detection of temperature-induced magnetization dynamics of molecular spin systems.

The development and technological applications of molecular spin systems require versatile experimental techniques to characterize and control their static and dynamic magnetic properties. In the latter case, bulk spectroscopic and magnetometric techniques, such as AC magnetometry and pulsed electron paramagnetic resonance, are usually employed, showing high sensitivity, wide dynamic range, and flexibility. They are based on creating a nonequilibrium state either by changing the magnetic field or by applying resonant microwave radiation. Another possible source of perturbation is a laser pulse that rapidly heats the sample. This approach has proven to be one of the most useful techniques for studying the kinetics and mechanism of chemical and biochemical reactions. Inspired by these works, we propose an inductive detection of temperature-induced magnetization dynamics as applied to the study of molecular spin systems and describe the general design and construction of a particular induction probehead, taking into account the constraints imposed by the cryostat and electromagnet. To evaluate the performance, several coordination compounds of VO2+, Co2+, and Dy3+ were investigated using low-energy pulses of a terahertz free electron laser of the Novosibirsk free electron laser facility as a heat source. All measured magnetization dynamics were qualitatively or quantitatively described using a proposed basic theoretical model and compared with the data obtained by alternating current magnetometry. Based on the results of the research, the possible scope of applications of inductive detection and its advantages and disadvantages in comparison with standard methods are discussed.

The increase of europium-based OLED luminance through reducing the excited state lifetime by mixed-ligand complex formation.

An approach to the luminance increase of the europium-based OLED is proposed through the formation of the mixed-ligand complex. The introduction of two diverse anionic ligands around one europium ion forming a mixed-ligand complex is confirmed by powder X-ray diffraction, 1H and 19F NMR spectroscopy, MALDI MS spectroscopy, and luminescence spectroscopy. A decrease in the symmetry of the coordination environment leads to a 50% reduction of the lifetime of the excited state. The obtained OLEDs based on mixed ligand europium complexes are significantly superior in luminance to OLEDs based on individual complexes.

Structural Significance of Hydrophobic and Hydrogen Bonding Interaction for Nanoscale Hybridization of Antiseptic Miramistin Molecules with Molybdenum Disulfide Monolayers.

This paper reports an easy route to immobilize the antiseptic drug miramistin (MR) molecules between the sheets of molybdenum disulfide, known for excellent photothermal properties. Two hybrid layered compounds (LCs) with regularly alternating monolayers of MR and MoS2, differing in thickness of organic layer are prepared and studied by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) calculations and quantum theory of atoms in molecules (QTAIM) topological analysis. The obtained structural models elucidate the noncovalent interaction network of MR molecules confined in the two-dimensional spacing surrounded by sulfide sheets. It emerged that the characteristic folded geometry of MR molecule previously evidenced for pure miramistin is preserved in the hybrid structures. Quantification of the energetics of bonding interactions unveils that the most important contribution to structure stabilization of both compounds is provided by the weak but numerous CH…S bonding contacts. They are accompanied by the intra- and inter-molecular interactions within the MR layers, with dominating bonding effect of intermolecular hydrophobic interaction. The results obtained in the models provide a comprehensive understanding of the driving forces controlling the assembly of MR and MoS2 and may lead towards the development of novel promising MoS2-based photothermal therapeutic agents.

Solution-Processed OLED Based on a Mixed-Ligand Europium Complex.

An approach to increase the efficiency of europium-based OLEDs was proposed through the formation of a mixed-ligand complex. The design of a series of europium complexes, together with an optimization of the solution deposition, including the host selection, as well as the variation of the solvent and deposition parameters, resulted in a noticeable increase in OLED luminance. As a result, the maximum luminance of the Eu-based OLED reached up to 700 cd/m2, which is one of the highest values for an Eu-based solution-processed OLED. Finally, its stability was investigated.

A 50% increase in the terbium-based OLED luminance through reducing the excited-state lifetime due to the introduction of gold nanoparticles.

An increase in the efficiency for a terbium-based OLED was achieved by introducing gold nanoparticles into the PEDOT:PSS hole injection layer and was mainly due to the improvement in carrier injection and the reduction of the excited-state lifetime. The introduction of plasmon-resonant gold nanoparticles resulted in a 50% increase in the Tb(czb)3TDZP luminance, which reached 480 cd m-2 and is the highest result for OLEDs based on aromatic carboxylates.

Field-Induced Slow Magnetic Relaxation in CoII Cyclopropane-1,1-dicarboxylates.

New CoII substituted malonate field-induced molecular magnets {[Rb6Co3(cpdc)6(H2O)12]∙6H2O}n (1) and [Cs2Co(cpdc)2(H2O)6]n (2) (where cpdc2- stands for cyclopropane-1,1-dicarboxylic acid dianions) were synthesized. Both compounds contain mononuclear bischelate fragments {CoII(cpdc)2(H2O)2}2- where the quasi-octahedral cobalt environment (CoO6) is complemented by water molecules in apical positions. The alkali metal atoms play the role of connectors between the bischelate fragments to form 3D and 2D polymeric structures for 1 and 2, respectively. Analysis of dc magnetic data using the parametric Griffith Hamiltonian for high-spin CoII supported by ab initio calculations revealed that both compounds have an easy axis of magnetic anisotropy. Compounds 1 and 2 exhibit slow magnetic relaxation under an external magnetic field (HDC = 1000 and 1500 Oe, respectively).

NIR luminescence thermometers based on Yb-Nd coordination compounds for the 83-393 K temperature range.

Multimetallic neodymium-ytterbium-gadolinium compounds with 9-anthracenate and 9-acridinate anions were tested in order to create the first luminescent thermometer for elevated temperatures. High luminescence intensity and high signal resolution were reached thanks to the concentration quenching elimination due to the partial substitution of the emitting ions with Gd3+. As a result, NIR emitting materials for luminescence thermometry in the wide temperature range (83-393 K) based on lanthanide coordination compounds (CCs) were obtained. The best thermometric properties among the studied systems were demonstrated by Yb0.02Nd0.12Gd0.86(ant)3, and its temperature sensitivity reached 1.8% K-1 in the temperature range of 293-393 K.

Record efficiency of 1000 nm electroluminescence from a solution-processable host-free OLED.

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.

Change in the Electronic Structure of the Cobalt(II) Ion in a One-Dimensional Polymer with Flexible Linkers Induced by a Structural Phase Transition.

A new 1D-coordination polymer [Co(Piv)2(NH2(CH2)6NH2)]n (1, Piv is Me3CCO2- anion) was obtained, the mononuclear fragments {Co(O2CR)2} within which are linked by µ-bridged molecules of hexamethylenediamine (NH2(CH2)6NH2). For this compound, two different monoclinic C2/c (α-1) and P2/n (ß-1) phases were found at room temperature by single-crystal X-ray diffraction analysis, with a similar structure of chains and their packages in unit cells. The low-temperature phase (γ-1) of crystal 1 at 150 K corresponds to the triclinic space group P-1. As the temperature decreases, the structural phase transition (SPT) in the α-1 and ß-1 crystals is accompanied by an increase in the crystal packing density caused by the rearrangements of both H-bonds and the nearest ligand environment of the cobalt atom ("octahedral CoN2O4 around the metal center at room temperature" → "pseudo-tetrahedral CoN2O2 at 150 K"). The SPT was confirmed by DSC in the temperature range 210-150 K; when heated above 220 K, anomalies in the behavior of the heat flow are observed, which may be associated with the reversibility of SPT; endo effects are observed up to 300 K. The SPT starts below 200 K. At 100 K, a mixture of phases was found in sample 1: 27% α-1 phase, 61% γ-1 phase. In addition, at 100 K, 12% of the new δ-1 phase was detected, which was identified from the diffraction pattern at 260 K upon subsequent heating: the a,b,c-parameters and unit cell volume are close to the structure parameters of γ-1, and the values of the α,ß,γ-angles are significantly different. Further heating leads to a phase transition from δ-1 to α-1, which both coexist at room temperature. According to the DC magnetometry data, during cooling and heating, the χMT(T) curves for 1 form a hysteresis loop with ~110 K, in which the difference in the χMT values reaches 9%. Ab initio calculations of the electronic structure of cobalt(II) in α-1 and γ-1 have been performed. Based on the EPR data at 10 K and the ab initio calculations, the behavior of the χMT(T) curve for 1 was simulated in the temperature range of 2-150 K. It was found that 1 exhibits slow magnetic relaxation in a field of 1000 Oe.

Europium complexes with dinitropyrazole: unusual luminescence thermal behavior and irreversible temperature sensing.

Europium 3,5-dinitropyrazole complexes demonstrate an unusual luminescence behavior upon heating, i.e. there is a noticeable increase of the luminescence intensity beyond a temperature of 200 °C. We propose and successfully demonstrate the possibility of using this phenomenon for sensing overheating above this temperature. An on/off ratio of 37 is reached.

Identifying lifetime as one of the key parameters responsible for the low brightness of lanthanide-based OLEDs.

OLEDs based on lanthanide complexes have decisive optical advantages but are hampered by low brightness. Despite the efforts to optimize several parameters such as quantum yield and charge carrier mobility, there seems to be another key parameter that hinders their performances. Experimental data are therefore collected for mixed-ligand europium complexes with bathophenanthroline and different classes of anionic ligands and screened to identify the key parameter responsible for this situation, which turns out to be the long lifetime of their excited states. A broad literature search supports this conclusion, showing that lanthanide complexes are inferior to other classes of OLED emitters often because of their long lifetimes; furthermore, among a series of lanthanide complexes, the best results are achieved for those with the shortest lifetimes, even though they suffer from low quantum yields.

Eu(tta)3DPPZ-based organic light-emitting diodes: spin-coating vs. vacuum-deposition.

The effect of the emission layer deposition method on the characteristics of OLEDs was studied on the example of the europium mixed-ligand complex Eu(tta)3DPPZ (tta: 2-thenoyltrifluoroacetone, DPPZ: dipyrido[3,2-a:2'c,3'c-c]phenazine). The maximum brightnesses of both OLEDs almost coincided, though OLED based on the spin-coated layer operated at lower voltages. The reason for that was the higher density and smoothness of the solution-processed layer.

Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine.

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2-300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH2Cl2 solution was monitored by EPR spectroscopy.

Highly NIR-emitting ytterbium complexes containing 2-(tosylaminobenzylidene)-N-benzoylhydrazone anions: structure in solution and use for bioimaging.

Solution behaviour in DMSO using 1D and 2D NMR spectroscopy was performed for lanthanide complexes Ln(L)(HL) and Ln(HL)2Cl, containing non-macrocyclic 2-(tosylamino)-benzylidene-N-benzoylhydrazone (H2L), and the structure of [Yb(L)]+ cation in solution was determined. Based on the NMR data, the possibility to obtain novel complexes containing [Ln(L)2]- was predicted, which was successfully synthesized, and the crystal structure of K(C2H5OH)3[Yb(L)2] was determined. Thanks to its high quantum yield of NIR luminescence (1.3 ± 0.2%), high absorption, low toxicity, and the stability of its anion against dissociation in DMSO, K(H2O)3[Yb(L)2] was successfully used for bioimaging.

Novel Polymorph of Favipiravir-An Antiviral Medication.

Various solid forms of pharmaceutically important compounds exhibit different physical properties and bioactivity; thus, knowledge of the structural landscape and prediction of spontaneous polymorph transformations for an active pharmaceutical ingredient is of practical value for the pharmaceutical industry. By recrystallization from ethyl acetate, a novel polymorph of 6-fluoro-3-hydroxypyrazine-2-carboxamide (trademark favipiravir, RNA polymerase inhibitor) was obtained and characterized using differential scanning calorimetry (DSC), infra-red spectroscopy and powder X-ray diffraction (XRD) analysis. The favipiravir molecule in two polymorphs realizes similar H-bonding motifs, but the overall H-bonded networks differ. Based on periodic density functional theory calculations, the novel tetragonal polymorph with two interpenetrated H-bonded networks is slightly less stable than the orthorhombic one with the zst topology of the underlying H-bonded net that is in accord with experimentally observed powder XRD patterns of slow conversion of the tetragonal phase to the orthorhombic one. However, topological analysis of net relations revealed that no transformations can be applied to convert H-bonded networks in the experimental unit cells, and DSC data indicate no solid-state reactions at heating.

Complexes of Cobalt(II) Iodide with Pyridine and Redox Active 1,2-Bis(arylimino)acenaphthene: Synthesis, Structure, Electrochemical, and Single Ion Magnet Properties.

Complexes [(dpp-BIAN)0CoIII2]·MeCN (I) and [(Py)2CoI2] (II) were synthesized by the reaction between cobalt(II) iodide and 1,2-bis(2,6-diisopropylphenylimino)acenaphthene (dpp-BIAN) or pyridine (Py), respectively. The molecular structures of the complexes were determined by X-ray diffraction. The Co(II) ions in both compounds are in a distorted tetrahedral environment (CoN2I2). The electrochemical behavior of complex I was studied by cyclic voltammetry. Magnetochemical measurements revealed that when an external magnetic field is applied, both compounds exhibit the properties of field-induced single ion magnets.

Probing Hydrogen-Bonding Properties of a Negatively Charged MoS2 Monolayer by Powder X-ray Diffraction and Density Functional Theory Calculations.

The contributions of various noncovalent interactions in stabilization of the assembled and delaminated MoS2-hexamethylenetetramine (HMTA)-layered compound resulted from the assembly of protonated HMTA molecules and negatively charged 1T-MoS2 monolayers have been considered on the basis of powder X-ray diffraction pattern modeling, density functional theory calculations, and atoms in molecules quantum theory analysis. The structure with HMTA cations involved in NH···S bonding with MoS2 layers was concluded to be more advantageous than the alternative one with NH···N bonding between the cations. Delamination was demonstrated to essentially influence the hierarchy of interactions and leads to significant strengthening of the NH···S hydrogen bond established between HMTA and the MoS2 monolayer surface. The method applied in this study for evaluation of the monolayer MoS2 properties on the basis of the 3D structure of the MoS2-organic compound is expected to be helpful to gain insights into the interactions occurring in many MoS2-based systems.

Pot, atom and step economic (PASE) assembly of salicylaldehydes, malononitrile dimer and 4-hydroxypyridine-2(1H)-ones into medicinally relevant 5H-chromeno[2,3-b]pyridine scaffold.

The new multicomponent reaction (MCR) has been found: one-pot selective and efficient formation of the new 5-(4-hydroxy-2-oxo-1,2-dihydropyridin-3-yl)-substituted 5H-chromeno[2,3-b]pyridines in 61-97% yields directly from simple and easily available salicylaldehydes, malononitrile dimer and 4-hydroxypyridine-2(1H)-ones in small amount of pyridine-ethanol catalyst/solvent system. This complex "domino" transformation includes Knoevenagel condensation of salicylaldehyde with malononitrile dimer, Michael addition of 4-hydroxypyridine-2(1H)-one, double Pinner-type reaction cyclization and isomerization with following protonation. This facile multicomponent process opens a new way to 5-(4-hydroxy-2-oxo-1,2-dihydropyridin-3-yl)-substituted 5H-chromeno[2,3-b]pyridine systems, which are promising compounds for the treatment for human inflammatory TNFα-mediated diseases and different biomedical applications.

One-pot five-component high diastereoselective synthesis of polysubstituted 2-piperidinones from aromatic aldehydes, nitriles, dialkyl malonates and ammonium acetate.

A novel five-component diastereoselective synthesis of polysubstituted 2-piperidinones is reported. The Knoevenagel condensation-Michael addition-Mannich cascade of two equivalents of aromatic aldehydes, nitriles, dialkyl malonates and ammonium acetate or aqueous ammonia in alcohols provides convenient access to alkyl (3SR,4RS,6SR)-5,5-dicyano-2-oxo-4,6-diarylpiperidine-3-carboxylates with three stereocenters in 52-90% or dialkyl (2SR,3RS,4RS,5SR)-2,4-diaryl-3-cyano-6-oxopiperidine-3,5-dicarboxylates with four stereocenters in 38-88%. The formation of products was highly stereoselective, with only one diastereomer formed. Ammonium acetate or aqueous ammonia plays a role both as a catalyst and as a nitrogen source. 2,4,6-triaryl-3,3,5,5-tetracyanopiperidines were obtained as a side products in the reactions with nitro-substituted aldehydes or with ethyl and n-propyl cyanoacetates. A series of 14 2-piperidinones and piperidines was assessed for antimicrobial activity against a panel of five bacteria and two fungi; no significant activity was observed. Two side piperidines with nitro substituents in aromatic ring possess bacteriostatic action against S. aureus ATCC 43300 and A. baumannii ATCC 19606 at 32 ug/mL.

On the development of a new approach to the design of lanthanide-based materials for solution-processed OLEDs.

The targeted design of lanthanide-based emitters for solution-processed organic light-emitting diodes (OLEDs) resulted in obtaining an NIR OLED with one of the highest efficiencies among ytterbium-based solution-processed OLEDs (30 µW W-1). The design was aimed at the combination of high luminescence efficiency with solubility and charge carrier mobility. The latter was achieved thanks to the introduction of the purposefully selected neutral ligands, which combine electron mobility and the ability to sensitize lanthanide luminescence. Besides, the HOMO and LUMO energies and charge carrier mobility of solution-processed thin films of coordination compounds were measured experimentally for the first time, and novel highly luminescent europium-based materials with PLQYs of up to 80% and purely NIR luminescent ytterbium complexes were obtained.