| Through self-assembly of the Salen-type Schiff-base ligand H2L~1 (N, N’-bis(salicylidene)cyclohexane-1,2-diamine) and one of two β-diketonate ligands HL2 ((Z)-3-methyl-1-phenyl-4-(2,2,2-trifluoro-1-hydroxyethylidehe)-1H-pyrazol-5(4H)-one) and HL3 (4,4,4-trifluoro-l-(thiophen-2-yl)butane-1,3-dione) with Zn(OAc)2·2H2O and LnCl3·6H2O (Ln=La, Nd, Yb, Er, Eu, Tb or Gd) in the presence of Py (pyridine) or 4-vinyl-Py (4-vinyl-pyridine), three series of 18 heterodinuclear rare earth complexes:(Series I) [Zn(L~1)*Py)Ln(L2)3] (Ln=La,1; Nd,2; Yb,3; Er,4; Gd,5; Eu,6; Tb,7), (Series Ⅱ) [Zn(L~1)(4-vinyl-Py)Ln(L2)3] (Ln=La,8; Nd,9; Yb,10; Er,11; Gd,12; Eu,13; Tb,14) and (Series Ⅲ) (Zn(L~1)(4-vinyl-Py)Ln(L3)3] (Ln=La,15; Gd,16;Eu,17;Tb,18) were obtained, respectively. Besides, structural characterization by EA, FT-IR,1H NMR and XRD, their optical properties were studied.In the meantime, the series of hydrid materials PMMA@[Zn(L~1)(Py)Ln(L2)3] (Ln=La, 1; Nd,2; Yb,3; Er,4; Gd,5) were obtained through physical doping of [Zn(L~1)(Py)Ln(L2)3] (Ln=La,1; Nd,2; Yb,3; Er,4; Gd,5) into PMMA (polymethyl methacrylate)。Secondly, using one of compounds [Zn(L~1)(4-vinyl-Py)Ln(L2)3] (Ln=La,8; Nd,9; Yb,10; Er,11; Gd, 12) and [Zn(L~1)(4-vinyl-Py)Ln(L3)3] (Ln=La,15; Gd,16; Eu,17) with one active vinyl group as the complex monomer, its copolymerization with MMA (methyl methacrylate), NVK (vinylcarbazole) or ST (styrene) in the presence of AIBN (2,2-azobisisobutyronitrile) afforded grafting-type hybrid materials Poly(MMA-co-[Zn(L~1)(4-vinyl-Py)Ln(L2)3]) (Ln= La,8; Nd,9; Yb,10; Er,11; Gd,12), Poly(MMA-co-[Zn(L~1)(4-vinyl-Py)Ln(L3)3]) (Ln=La, 15; Gd,16; Eu,17), Poly(NVK-co-[Zn(L~1)(4-vinyl-Py)Ln(L3)3]) (Ln=La,15; Gd,16; Eu, 17) and Poly(ST-co-[Zn(L~1)(4-vinyl-Py)Ln(L3)3]) (Ln=La,15; Gd,16; Eu,17), respectively. Finally, both of their characterization from FT-IR,1H NMR, TG, PXRD and GPC and their physical properties including optical property, thermal stability were explored. |
