Research Of New Zn(Ⅱ)-Ln(Ⅲ) Schiff Base Hybrid Luminescent Materials

Because the near infrared luminescent materials have a wide range of applications in the lighting, display imaging, medical radiation and other fields, rare earth ion (Nd3+and Yb3+, Er3+) complexes luminescent material of near infrared attracted many scholars. In order to change the low extinction coefficient of rare earth ions for f-f orbital part forbidden transition. People usually adopt the chromophore having the strong absorption of light as an antenna to sensitization near-infrared luminescence of rare earth ions, by adopting Zn2+, Cr3+metal ions complexes as antenna to sensitization of rare earth ions near-infrared luminescence.In this paper, we adopts the zinc ions schiff base complexes as antenna for sensitization of rare earth ion luminescence, designed and synthesized several series of new rare earth complexes and the new hybrid materials. Their structure can be determined by chemical analysis methods like EA、IR、1H-NMR、GPC and X-ray single crystal diffraction. In addition, the photophysical properties can be studied by UV-visible absorption spectra, near infrared and visible emission and excitation spectra.First of all, we were synthesized and prepared of the three series of transition metal and lanthanide metal hetero-binuclear complexes with new functional schiff base ligands.[ZnLnL (OAc)3](Ln=La,1; Ln=Nd,2; Ln=Yb,3; Ln=Er,4; Ln=Gd,5),[ZnLnL1(OAc)3](Ln=La,6; Ln=Nd,7; Ln=Yb,8; Ln=Er,9; Ln=Gd,10) and [ZnLnL2(OAc)3](Ln=La,11; Ln=Nd,12; Ln=Yb,13; Ln=Er,14; Ln=Gd,15). By chemical analysis methods like EA、 IR、1H-NMR、GPC and X-ray single crystal diffraction determination, their structures are characterized and their photophysical properties are also discussed.Second, In order to change the coordination environment of rare earth ions, we were synthesized and prepared of two series of transition metal and lanthanide metal hetero-binuclear complexes with new functional schiff base ligands.[ZnLnL (NO3)3epy](Ln=La,16; Ln=Nd,17; Ln=Yb,18; Ln=Er,19; Ln=Gd,20) and [ZnLnL2(NO3)3](Ln=La,21; Ln=Nd,22; Ln=Yb,23; Ln=Er,24; Ln=25, Gd). By chemical analysis methods like EA、IR>、1H-NMR、GPC and X-ray single crystal diffraction determination, their structures are characterized and their photophysical properties are also discussed.Moreover, in order to observe the effects of antenna effect to luminescence intensity and further synthesized bichromophore sandwich structure hetero-trinuclear metal complexes [Zn2LnL (NO3)2(DMF)](Ln=La,26; Ln=Nd,27; Ln=Yb,28; Ln=Er,29; Ln=Gd,30). By chemical analysis methods like EA、IR、1H-NMR、GPC and X-ray single crystal diffraction determination, their structures are characterized and their photophysical properties are also discussed.Finally, the compound1-10and monomer styrene (St), methyl methacrylate (MMA), N-vinyl carbazole (NVK) according to certain proportion reaction preparation good dispersion polymer luminescent material31to40,41to50and51to60, respectively. Complexes21-25and borneol olefin copolymerization preparation of the hybrid materials61-65. By chemical analysis methods like1H-NMR、GPC determination, their structures are characterized and their photophysical properties are also discussed.