Yan-Jun Hu

Synthesis and spectroscopic properties of some new difluoroboron bis-β-diketonate derivatives

Six new bis-β-diketones (RCOCH2CO-C7H7N-COCH2COR) were synthesized from 3,5-diacetyl-2,6-dimethylpyridine via Claisen condensation with the corresponding esters, and then reacted with boron trifluoride etherate to afford difluoroboron bis-β-diketonate derivatives. Their spectroscopic properties were investigated by UV-vis, FTIR, (1)H NMR and fluorescence spectroscopic techniques. It was found that these boron complexes exhibited violet or blue fluorescence emission at 422-445nm and possessed high extinction coefficients. The results indicate that the extending π-conjugation can increase the fluorescence intensity and quantum yield for these boron complexes. Especially, the compound 2b displayed the stronger fluorescence intensity and the highest fluorescence quantum yield (Φu=0.94) in these boron compounds. However, compounds 2c and 2d had the lower fluorescence intensity and quantum yield as a result of the heavy atom effect of the chlorine atom in the molecules.

Photoluminescence behavior of europium (III) complexes containing 1-(4-tert-butylphenyl)-3-(2-naphthyl)-propane-1,3-dione ligand

Three novel europium complexes with 1-(4-tert-butylphenyl)-3-(2-naphthyl)-propane-1,3-dione (TNPD) and 2,2-dipyridine (Bipy) or 1,10-phenan-throline (Phen) were synthesized and confirmed by FT-IR, (1)H NMR, UV-vis absorption and elemental analysis. Photoluminescence behavior of complexes Eu(TNPD)3, Eu(TNPD)3·Bipy and Eu(TNPD)3·Phen were investigated in detail. Their emission spectra exhibited the characteristic emission bands that arise from the (5)D0→(7)FJ (J=0-4) transitions of the europium ion in solid state. Meanwhile, the results of their lifetime decay curves indicated that only one chemical environment existed around the europium ion. The intrinsic luminescence quantum efficiency (η) and the experimental intensity parameters (Ωt) of europium complexes were determined according to the emission spectra and luminescence decay curves in solid state. The complex Eu(TNPD)3·Phen showed much longer lifetime (τ) and higher luminescence quantum efficiency (η) than complexes Eu(TNPD)3 and Eu(TNPD)3·Bipy.

Fluorescence quenching study of 2,6-bis(5-(4-methylphenyl)-1-H-pyrazol-3-yl)pyridine with metal ions

A novel bispyrazole derivative 2,6-bis(5-(4-methylphenyl)-1-H-pyrazol-3-yl)pyridine was synthesized and its structure was confirmed by (1)H NMR, FTIR, MS techniques and elemental analysis. The binding interactions of BMPP with Cd(2+), Co(2+), Pb(2+) and Cu(2+) ions were investigated in MeOH-H2O solution by fluorescence quenching technique at two temperatures (25 and 35°C). Their quenching constants KSV, binding constants K, binding sites n and thermodynamic parameters (ΔH, ΔG and ΔS) were determined. The results indicated that the metal ions quenched the intrinsic fluorescence of the bispyrazole by forming the bispyrazole-metal complexes and their quenching process was a static quenching mechanism. In addition, the process of interaction was spontaneous and mainly ΔS-driven.

SYNTHESIS AND ANTI-MICROBIAL ACTIVITIES OF 1,3,5-TRISUBSTITUTED-PYRAZOLE DERIVATIVES CONTAINING A PYRIDYL MOIETY

Claisen condensation of ethyl isonicotinate with different acetophenones gave the corresponding pyridyl-s-diketones, while the treatment with hydrazine hydrate yielded 3,5-disubstituted-1H-pyrazoles, which then converted 1,3,5-trisubstituted-pyrazole derivatives containing a pyridyl moiety by N-acylation with acyl chloride. The structures of all newly synthesized compounds are established by FTIR, 1H NMR, mass spectroscopy and elemental analysis, and in the case of compound 2e, analyzed by single-crystal X-ray diffraction further. The anti-microbial activities of the title compounds have been tested by disc diffusion method against Escherichia coli, Staphylococcus aureus, Pyricularia oryzae and Rhizoctnia solani. The results showed that compounds 3c and 4c exhibited good inhibitory activity against all the tested organisms.