Self-assembly Of Chrysin-6-sulfonate With Metal Ions And Crystal Structure

Chrysin is one of flavonoids widely spread in nature. It has extensive biological activities, such as antivirus, antioxidant, and anticancer. Supramolecular chemistry is an important extension of the chemical field. Its object is the multimolecular entities assembled by the weak no-covalence interaction between molecules. It can be defined as "extended coordination chemistry" and the bridge linked the coordination chemistry with supramolecular chemistry is the intermolecular forces in the coordination complex. In order to improve the coordination abilities of chrysin with metal ions, the chrysin was sulfonated. Two chrysinsulfonates, chrysin-6-sulfonate and chrysin-8-sulfonate were obtained. Chrysin-6-sulfonate acted a ligand and self-assembled with Zn(II), Cd(II), Ba(II), Cu(II). 4 kinds of the sulfonate coordination complexes were synthesized and determined. The crystal structures and supramoecular forces were studied, In addition to, the mechanism of twice Baker-Venkataraman rearrangement was discussed.Firstly, the classification and complexing action with metal ions of flavonoids, pharmacological actions of chrysin and supramolecular self-assembly were reviewed. Secondly, the mixture of chrysin-6-sulfonate and chrysin-8-sulfonate was obtained by sulfonated chrysin. By the method of coordination and depolymerization, two chrysinsulfonates were separated. The ligand, sodium 5,7-bihydroxyflavone-6-sulfonate coordinates with Zn( II), Cd( II), Ba( II), Cu( II), and 4 sulfonate complexes were obtained including a dinuclear zinc complex, a tetranuclear cadmium complex, a barium coordination polymer and a copper complex. They were characterized by ~1H NMR, IR and X-ray single-crystal diffraction analysis. The crystal structures and supramolecular forces of four complexes were discussed and the photoluminescent phenomena of the dinuclear zinc complex and the tetranuclear cadmium complex were observed and the photoluminescent mechanisms were discussed.Finally, 2,4,6-tribenzoyloxyacetophenone, chrysin and DBM were synthesized in the synthetic course of chrysin. And the mechanism of twice Baker-Venkataraman rearrangement was discussed.The water solubility and coordination ability of chrysin were strengthened byintroduced a sulfo-group in 6- or 8- position of chrysin. The bidentate ligand, chrysin-6-sulfonate, self-assembled with Zn(II), Cd(II), Ba(II) and Cu(II), and formed supramolecular complexes by coordination interactions, electrostatic interactions, hydrogen interactions and n-n stacking interactions. The dinuclear zinc complex and the tetranuclear cadmium complex have photoluminescent phenomena. It is possible to make developing new drug and novel photoluminescent materials because of the synthesis of the water-solubility ligand of flavonoids.