Synthesis, Structure, Spectral-Luminescent Properties, and Biological Activity of Chlorine-Substituted N-[2-(Phenyliminomethyl)phenyl]-4-methylbenzenesulfamide and Their Zinc(II) Complexes.

New azomethine compounds of 2-(N-tosylamino)benzaldehyde or 5-chloro-2-(N-tosylamino)benzaldehyde and the corresponding chlorine-substituted anilines, zinc(II) complexes based on them have been synthesized. The structures of azomethines and their complexes were determined by elemental analysis, IR, 1H NMR, X-ray spectroscopy, and X-ray diffraction. It is found that all ZnL2 complexes have a tetrahedral structure according to XAFS and X-ray diffraction data. The photoluminescent properties of azomethines and zinc complexes in methylene chloride solution and in solid form have been studied. It is shown that the photoluminescence quantum yields of solid samples of the complexes are an order of magnitude higher compared to the solutions and range from 11.34% to 48.3%. The thermal properties of Zn(II) complexes were determined by thermal gravimetric analysis (TGA) and differential scanning calorimetry. The TGA curves of all the compounds suggest their high thermal stability up to temperatures higher than 290 °C. The electrochemical properties of all complexes were investigated by the cyclic voltammetry method. The multilayered devices ITO/PEDOT:PSS/NPD/Zn complex/ TPBI/LiF/Al with wide electroluminescence (EL) color range spanning the range from bluish-green (494 nm) to green (533 nm) and the high values of brightness, current and power efficiency were fabricated. The biological activity of azomethines and zinc complexes has been studied. In the case of complexes, the protistocidal activity of the zinc complex with azomethine of 5-chloro-2-(N-tosylamino)benzaldehyde with 4-chloroaniline was two times higher than the activity of the reference drug toltrazuril.

Zinc Complexes of Fluorosubstituted N-[2-(Phenyliminomethyl)phenyl]-4-methylbenzenesulfamides: Synthesis, Structure, Luminescent Properties, and Biological Activity.

Mono-, di-, and trifluorophenyl substituted in different positions of amine fragments bis [2-[[(E)-((fluorophenyl)iminomethyl]-N-(p-tolylsulfonyl)anilino]zinc(II) complexes were synthesized. Their crystal structure, photo- and electroluminescent properties, and protistocidal, fungistatic, and antibacterial activities were studied. It has been shown that the introduction of fluorine atoms and an increase in their number in the ligand structure of the resulting metal complexes promote the luminescence quantum yields and values of performance and brightness in EL cells compared to their previously studied chlorine-substituted analogs.

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.

The peculiarities of complex formation and energy transfer processes in lanthanide complexes with 2-(tosylamino)-benzylidene-N-benzoylhydrazone.

Depending on the local excess of lanthanide ions (Ln = Lu, Yb, Er, Dy, Tb, Gd, Eu, Nd) or 2-(tosylamino)-benzylidene-N-benzoylhydrazone (H2L), lanthanide complexes, containing either a mono-deprotonated ligand (Ln(HL)2X, X = Cl, NO3) or both mono- and dideprotonated ligands (Ln(L)(HL)), were preparatively obtained. The crystal structures of Lu(HL)2Cl, Yb(L)(HL)(H2O)2, Yb(L)(HL)(EtOH)2(H2O) and Er(L)(HL), determined by single crystal diffraction data or from powder diffraction data using Rietveld refinement, have shown the surprising resemblance. The study of luminescence temperature dependence of Eu(HL)2Cl and Eu(L)(HL) showed that europium luminescence is quenched by thermally-activated 5D0 → T1 energy transfer. Luminescent thermometers based on these complexes demonstrated the sensitivity of up to 7.7% at 85 K which is the highest value above liquid-nitrogen temperatures obtained to date.

Synchrotron powder diffraction in a systematic study of 4'-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5 complexes.

The crystal structures of two compounds, CuL(2) and LiNCS.HL [HL = 4'-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5], have been determined from synchrotron powder diffraction data. Both compounds crystallize in the monoclinic space group P2(1)/c and with one molecule in the asymmetric unit. In CuL(2) the four N atoms of two bidentate L ligands coordinate the Cu(II) ion in a distorted tetrahedral geometry with Cu-N distances of 1.98 (5)-2.05 (5) A, while two O atoms from two sulfoxide groups complete the distorted octahedral Cu coordination [Cu-O 2.64 (4), 2.74 (4) A]. In LiNCS.HL, lithium is coordinated by all five ether O atoms with Li-O distances of 2.03 (3)-2.50 (3) A and an N atom from the thiocyanate moiety [Li-N 1.98 (3) A] in a distorted pentagonal pyramidal geometry. Preliminary potentiometric selectivity measurements for ion-selective electrodes (ISEs) based on CuL(2) and ZnL(2) demonstrated significant differences in their selectivity. In order to find a possible reason for this, theoretical calculations at the DFT (B3LYP) level were performed. These calculations used the crystal structures of CuL(2), LiNCS.HL, ZnL(2) and HL as input geometries for the minimum energy optimization in vacuo. The results indicate that in ML(2) complexes (M = Cu, Zn) the electronic structure of the metal ion determines the spatial orientation of benzo-15-crown-5 macrocycles, and their different orientation in CuL(2) and ZnL(2) results in different potentiometric selectivities of ISEs based on these compounds.