Eu³⁺- and Tb³⁺-Based Coordination Complexes of Poly(<i>N</i>-Isopropyl,<i>N</i>-methylacrylamide-<i>stat</i>-<i>N,N</i>-dimethylacrylamide) Copolymer: Synthesis, Characterization and Property

Abstract

This contribution reports the syntheses, structural analyses and properties of europium (Eu3+)- and terbium (Tb3+)-based coordination complexes of poly(N-isopropyl,N-methylacrylamide-stat-N,N-dimethylacrylamide) (poly(iPMAm-stat-DMAm)) copolymer, named as poly-Eu(III) and poly-Tb(III), respectively. In greater detail, poly(iPMAm85-stat-DMAm15) is first prepared by random copolymerization of N-isopropyl,N-methylacrylamide (iPMAm) and N,N-dimethylacrylamide (DMAm) via group transfer polymerization (GTP). Next, poly(iPMAm85-stat-DMAm15) is used as the polymer matrix for chelating with Eu3+ and Tb3+ cations at its side amide groups, to produce poly-Eu(III) and poly-Tb(III). Their structural characterizations by FT-IR spectroscopy and XPS confirm the formation of polymeric complexes. The study on their fluorescence emission characteristics and luminescence lifetime demonstrates that Poly-Eu(III) shows four strong emission peaks at 578, 593, 622, and 651 nm, which are responsible for the electron transitions from the excited 5D0 state to the multiplet 7FJ (J = 0, 1, 2, 3) states, respectively, and poly-Tb(III) also displays four emission peaks at 489, 545, 588, and 654 nm, mainly due to the electron transitions of 5D4 → 7Fi (i = 6, 5, 4, 3). The luminescence lifetimes of poly-Eu(III) (τpoly-Eu(III)) and poly-Tb(III) (τpoly-Tb(III)) are determined to be 4.57 and 7.50 ms, respectively. In addition, in aqueous solutions, poly-Eu(III) and poly-Tb(III) are found to exhibit thermoresponsivity, with their cloud temperatures (Tcs) locating around 36.4 and 36.8 °C, respectively. Finally, the cytotoxicity study on the human colon carcinoma cells LoVo and DLD1 suggests that the luminescent Eu3+ and Tb3+ in the chelated state with poly(iPMAm-stat-DMAm) show much better biocompatibility and lower toxicity than their inorganic salts.

Keywords

• group transfer polymerization
• rare earth complexes
• thermoresponsive
• fluorescent property
• cell viability