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

Six new bis-ß-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-ß-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.

Synthesis, characterization and fluorescence properties of boron difluoride pyridyl-ß-diketonate derivatives.

Five pyridyl-ß-diketones were synthesized by Claisen condensation of ethyl nicotinate with various aryl methyl ketones in benzene in the presence of sodium amide as the base, and then reacted with boron trifluoride diethyl etherate in dichloromethane to afford some new boron difluoride pyridyl-ß-diketonate derivatives. The compounds obtained were characterized using FTIR, (1)H NMR, elemental analysis and mass spectrometry. Their optical properties were studied in DMF by UV-vis absorption and fluorescence spectroscopy. The results showed that these boron complexes exhibited intense fluorescence in the blue-green region (420-490 nm) under UV radiation with a relatively high quantum yield. Especially, compounds 4b and 5b displayed much higher quantum yield as compared to compounds 1b, 2b and 3b.