Thermal, spectroscopic, electrochemical, and electroluminescent characterization of malononitrile derivatives with triphenylamine structure.

Three push-pull molecules with linear, quadrupolar and tripodal arrangements, consisting of triphenylamine (electro-donor) substituted with malononitrile groups (electro-acceptor), were synthesized with high yield by a simple procedure. Impact of the number of malononitrile substituents on optoelectronic properties was investigated with cyclic voltammetry, absorption and emission spectroscopy, as well as density functional theory calculation. The derivatives formed amorphous materials and exhibited low energy band gaps ranging from 2.06 to 2.49 eV. UV-Vis absorption and photoluminescence emission spectra were investigated in solutions (CHCl3, NMP) and in solid-state as thin films and two kinds of blends (with PMMA and PVK:PBD). Quantum yield of photoluminescence was dependent on the molecule structure, solvent, and solid-state layer formulation. The compounds exhibited high photoluminescence quantum yield in the range of 15-42% and 12-59% in solid-state as film and blend with PMMA (1 wt%), respectively, being promising for applications in light emitting diodes. The diodes with active layer consisting of neat derivatives and compounds molecularly dispersed in PVK:PBD (50:50 wt%) matrix showed orange and green electroluminescence.

Polycyclic aromatic hydrocarbons connected with Schiff base linkers: Experimental and theoretical photophysical characterization and electrochemical properties.

A series of polyaromatic hydrocarbons with anthracene, phenanthrene and pyrene units connected with Schiff base junctions were synthesized via condensation of p-phenylenediamine and hydrazine with selected aldehydes. The effect of both hydrocarbon structures and presence of N-N- or phenyl- linked diimines on properties of the prepared azines and azomethines was analyzed. The obtained compounds were soluble in common organic solvents and melted in the range of 226-317°C. Their photophysical and electrochemical properties were investigated by UV-vis, photoluminescence spectroscopies and cyclic voltammetry (CV), respectively. Moreover, a density functional theory (DFT) was applied for calculation of their electronic and geometric structures as well as absorption and emission spectra. Additionally, their electron acceptor activity was preliminary tested in photovoltaic experiment.

New anthracene-based Schiff bases: Theoretical and experimental investigations of photophysical and electrochemical properties.

The new Schiff bases bearing anthracene unit were synthesized from 2-aminoanthracene and various aldehydes such as: benzaldehyde, 4-(diphenylamino)benzaldehyde, 9-phenanthrenecarboxaldehyde, 9-anthracenecarboxaldehyde, and biphenyl-4-carboxaldehyde, 2-naphthaldehyde. Resulted azomethines were characterized by IR, NMR (1H and 13C), elemental analysis and UV-vis spectroscopy. The imine consists of anthracene and biphenyl moieties exhibited liquid crystal properties and their nematic phase showed Schlieren texture. The photoluminescence measurements carried out in solution and in solid state as blend with PMMA revealed the ability of the imines to emission of the blue light with quantum yield efficiency in the range of 2.18-6.03% in blend. Based on the electrochemical experiment they showed value of energy gap (Eg) in the range of 2.5-2.7eV. Additionally, density functional theory (DFT) was applied for calculations of both electronic structure and spectroscopic properties of synthesized Schiff bases. Moreover, the results obtained from preliminary tests of application of the azomethines in organic photovoltaic (OPV) devices confirmed their electron acceptor character.

Comparative studies of structural, thermal, optical, and electrochemical properties of azines with different end groups with their azomethine analogues toward application in (opto)electronics.

Two series of azines and their azomethine analogues were prepared via condensation reaction of benzaldehyde, 2-hydroxybenzaldehyde, 4-pyridinecarboxaldehyde, 2-thiophenecarboxaldehyde, and 4-(diphenylamino)benzaldehyde with hydrazine monohydrate and 1,4-phenylenediamine, respectively. The structures of given compounds were characterized by FTIR, (1)H NMR, and (13)C NMR spectroscopy as well as elemental analysis. Optical, electrochemical, and thermal properties of all compounds were investigated by means of differential scanning calorimetry (DSC), UV-vis spectroscopy, stationary and time-resolved photoluminescence spectroscopy, and cycling voltammetry (CV). Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated theoretically by density functional theory (DFT). Influence of chemical structure of the compounds on their properties was analyzed.

Characterization and optical properties of oligoazomethines with triphenylamine moieties exhibiting blue, blue-green and green light.

New photoluminescence oligoazomethines possessing both hole and electron-transporting units in the main chain were synthesized. Triphenylamine (TPA) was used as the electron-donating group, while 4,4'-diaminooctafluorobiphenyl, 4,4'-(hexafluoro-isopropylidene)dianiline, 4-aminophenylsulfone, 4,4'-(4,4'-isopropylidenediphenyl-1,1'diyldioxy)dianiline and 2,5-bis(4-aminophenyl)-1,3,5-oxadiazole were used as the electron-acceptor or as the electron-donating group. The bifunctional oligomers (D-pi-A and D-pi-D) were soluble in some organic solvents such as chloroform, DMA, HMPA, NMP and formed transparent films on glass support. All oligomers exhibit high glass transition temperature in the range of 188-227 degrees C as determined by differential scanning calorimetry (DSC). The photoluminescence (PL) emission maximum peaks of the oligomers in solution are in the range of 459-552 nm (2.70-2.25 eV) corresponding to blue, blue-green or green light. The solvatochromic and protonation behavior of the oligomers in two solvents (DMA, chloroform) were detected. Oligomers protonated with methanesulfonic acid (MSA) are hypsochromically shifted with respect to the PL spectra of the pristine oligomers measured in solution. Relative PL intensity of the oligomers investigated in chloroform solution was found in the range of 0.10-0.50%, while for protonated ones it was detected in the range of 33-50% in relation to 9,10-diphenylanthracene. Blends of the oligoazomethines with poly(methylmethacrylate) (PMMA) (0.1%, w/w) emitted blue light. Thin films were also doped with iodine. Calculated energy gap for the undoped films following the Tauc relation was in the range of 2.46-2.69 eV while for the iodine doped oligomers in the range of 1.76-2.38 eV was found.

Synthesis and characterization of polyketanils with 3,8-diamino-6-phenylphenanthridine moieties exhibiting light emitting properties molecular and supramolecular engineering concept.

Relationship between structures and properties of new conjugated polyketanils (PKs) with special architectures, synthesized from three diketones, i.e. p-dibenzoylbenzene, dibenzyl, trans-1,2-dibenzoylethylene and 3,8-diamino-6-phenylphenanthridine, was investigated. The photoluminescence (PL) of green, yellow and red emitting light polymers and their blend was studied. These included the effects of excitation wavelength, concentration and film thickness on the PL. Photoluminescence properties of the PKs before and after protonation with 10-Camphorsulfonic acid (CSA) were tested. The structure formation of (PKs)(1)(CSA)(2) complexes are discussed on the basis of FTIR spectroscopy.

Synthesis and in vitro antiproliferative activity of new 1,3-(oxytetraethylenoxy)-cyclotriphosphazene derivatives.

A new series of 1,3-(oxytetraethylenoxy)-cyclotriphosphazene derivatives containing aziridine or salicylaldehyde (2-hydroxybenzaldehyde) or its Schiff base units after condensation with 2-chloroethylamine and anthraquinone groups as co-substituents has been synthesized. Their cytostatic activity in vitro against the HL-60, A549 and HCV29T cancer cell lines has been studied. Some of the compounds exhibited antiproliferative activity in the range of the international criteria for synthetic agents (4 microg/ml) against the cell lines being tested.

Temperature investigations of E/Z isomers in ketimines based of p-dibenzoylobenzene with aniline and 2,6-dimethylaniline by infrared spectroscopy.

The reaction of aniline with p-dibenzoylobenzene (K1) can lead to Z/Z, Z/E and E/E isomers however the only Z/Z and E/E were formed. At room temperature these isomers may be separated, thus the corresponding FTIR spectra could be recorded. The observed bands were assigned and temperature investigations were lead to monitor the structural changes during heating Z and E forms of K1 from 20 to 240 degrees C. FTIR spectroscopy showed that the bigger changes of the Z form was observed with an increase of temperature. Similar experience was lead with the ketimine synthesized from 2,6-dimethylaniline and p-dibenzoylobenzene (K2) investigated as a mixture of isomers.

Similarities and differences between azomethines and ketimines: synthesis, materials characterization and structure of novel imines compounds.

Imines (ketimines and azomethines) derived from p-dibenzoylbenzene (DB) and terephthalic aldehyde (TA) and two aromatic amines: aniline and 2,6-dimethylaniline have been investigated. Compounds were synthesized via condensation of amines with carbonyl monomers in DMA or amine solution. When using DMA as a solvent, azomethines with high yields were obtained. On the other hand, the amines used as a monomers served also as an effective solvent for the synthesis of the ketanils. This different reactivity of the aldehyde and ketone groups in DMA and in amine depends on the dehydration mechanism being dominated by a kinetic process or thermodynamic one. On the basis of FTIR, 13C and 1H NMR, UV-vis spectra, thermal characteristic and theoretical calculations conclusions are drawn regarding the similarities and differences between azomethines and ketimines.

Synthesis and in vitro antileukemic activity of some new 1,3-(oxytetraethylenoxy)cyclotriphosphazene derivatives.

A new series of 1,3-(oxytetraethylenoxy)cyclotriphosphazene derivatives bearing 2-chloroethylamine or salicylaldehyde (2-hydroxybenzaldehyde) or its Schiff base (after condensation with 2-chloroethylamine) units and having also 2-naphthyl or anthraquinone groups as cosubstituents has been synthesized. The in vitro cytotoxic activity of these compounds against a panel of four cancer cell lines has been studied. Most of the compounds exhibited antiproliferative activity in the range of the international criterion for synthetic agents (4 microg/mL) against the MOLT4, L 1210, HL-60, and P388 cell lines chosen for testing.

Synthesis and in vitro cytostatic activity of some new 1,3-(oxytetraethylenoxy)-cyclotriphosphazatriene derivatives.

A series of cyclophosphazene crown ether derivatives bearing aziridinyl (ethylene imine) units and also 2-naphthyl or anthraquinone groups as co-substituents has been synthesized and their cytostatic activity against the panel of eight cancer cells in vitro has been studied. The substituents used exhibit different activities: alkylation (aziridinyl groups) and intercalation (naphtyl, anthraquinone groups) against DNA. These both interactions are supposed to enhance the efficiency of the cyclophosphazene crown ether derivatives studied as cytotoxic agents.