Abstract
Poly(4-vinyl pyridine-co-methyl methacrylate), PVM, was synthesized by radical copolymerization of 4-vinyl pyridine with methyl methacrylate. Afterward, the macromolecular Eu(III) complexes of general formula [Eu(β-diketonate)3(PVM)(H2O)], where β-diketonate = benzoylacetonate (BA), 1; dibenzoylmethanate (DBM), 2; thenoyltrifluoroacetonate (TTA), 3, were prepared and fully characterized by means of element analysis, thermal analysis, SEM, 1H NMR, 13C NMR, FT-IR, and UV-vis spectra. The macromolecular complexes can dissolve in many ordinary organic solvents (e.g. dimethylformamide, dimethylsulfoxide, and tetrahydrofuran), as well as emit strong red luminescence under ultraviolet light excitation. The room-temperature 5D0 lifetime and fluorescence quantum yield of 3 are 391 μs and 37%, respectively, which are far more than those of 1 (194 μs, 16%), 2 (160 μs, 18%), and Eu(TTA)3(H2O)2 (224 μs, 22%). The CIE coordinates of 1–3 are calculated as (0.49, 0.33), (0.62, 0.33) and (0.65, 0.34), respectively, demonstrating the promising utilization future of these complexes, especially the latter two, as luminescent functional materials used in large-area optical display.
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References
Binnemans K (2009) Lanthanide-Based Luminescent Hybrid Materials. Chem Rev 109:4283–4374
Smirnov VA, Philippova OE, Sukhadolski GA, Khokhlov AR (1998) Multiplets in Polymer Gels. Rare Earth Metal Ions Luminescence Study. Macromolecules 31:1162–1167
Yang C, Xu J, Ma J, Zhu D, Zhang Y, Liang L, Lu M (2012) An efficient long fluorescence lifetime polymer-based sensor based on europium complex as chromophore for the specific detection of F−, CH3COO−, and H2PO4−. Polym Chem 3:2640–2648
Zhang D, Gao B, Cui K (2016) Modifying polysulfone into a bidentate Schiff base type macromolecular ligand and study on photoluminescence property of polymer–rare earth complexes of Eu(III) and Tb(III). J Polym Res 23:266–278
Kusumaatmaja A, Ando T, Terada K, Hirohara S, Nakashima T, Kawai T, Terashima T, Tanihara M (2013) Synthesis and photoproperties of Eu(III)-bearing star polymers as luminescent materials. J Polym Sci Part A: Polym Chem 51:2527–2535
Zhang T, Xu Z, Qian L, Tao DL, Teng F, Gao X, Xu XR (2005) The condition for electroplex emission from an europium complex doped poly(N-vinylcarbazole). Chem Phys Lett 415:30–33
Hauser CP, Thielemann DT, Adlung M, Wickleder C, Roesky PW, Weiss CK, Landfester K (2011) Luminescent Polymeric Dispersions and Films Based on Oligonuclear Lanthanide Clusters. Macromol Chem Phys 212:286–296
Eliseevaa SV, Bünzli JCG (2010) Lanthanide luminescence for functional materials and bio-sciences. Chem Soc Rev 39:189–227
Stanley JM, Holliday BJ (2012) Luminescent lanthanide-containing metallopolymers. Coord Chem Rev 256:1520–1530
Xu CJ, Wan JT, Li BG (2013) Monochromatic light-emitting copolymer of methyl methacrylate and Eu-complexed 5-acrylamido-1,10-phenanthroline. Dyes Pigments 98:493–498
Chen XY, Yang X, Holliday BJ (2008) Photoluminescent Europium-Containing Inner Sphere Conducting Metallopolymer. J Am Chem Soc 130:1546–1547
Xu CJ, Li BG (2010) Synthesis and Characterization of Highly Luminescent Copolymers of Methyl Methacrylate and Eu-Complexed 5-Acryloxyethoxymethyl-8-hydroxyquinoline. Macromol Chem Phys 211:1733–1740
Wang LH, Wang W, Zhang WG, Kang ET, Huang W (2000) Synthesis and Luminescence Properties of Novel Eu-Containing Copolymers Consisting of Eu(III)−Acrylate−β-Diketonate Complex Monomers and Methyl Methacrylate. Chem Mater 12:2212–2218
Fan S, Fei X, Wang X, Tian J, Xu L, Yang P, Wang Y (2014) Synthesis and investigation of a photosensitive, europium-containing polymer. React Funct Polym 76:19–25
Li JY (2001). Modern Chemical Industry 21:13–16
Stanimirov S, Petkov I (2009) Photophysical properties of novel fluorescent poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes. Spectrochim Acta Part A: Mol Biomol Spectrosc 72:1127–1133
Liu D, Wang Z, Yu H, You J (2009) Fluorescence properties of novel rare earth complexes using carboxyl-containing polyaryletherketones as macromolecular ligands. Eur Polym J 45:2260–2268
Zhang X, Zhang Z, Liu L, Yu C, Lü X, Zhu X, Wong W-K, Jones RA (2015) Dual-nodal PMMA-supported Eu 3+ -containing metallopolymer with high color-purity red luminescence. Inorg Chem Commun 60:51–53
Wang QM, Yan B (2006) Assembly of luminescent hybrids from co-polymers bearing functional 4-vinyl pyridine and europium aromatic carboxylate. J Photochem Photobiol A Chem 177:1–5
de Sá GF, Malta OL, de Mello DC, Simas AM, Longo RL, Santa-Cruz PA, da Silva Jr EF (2000). Coord Chem Rev 196:165–195
Zhang XF, Xu CJ, Wan J (2014) Mono- and dinuclear europium(III) complexes with thenoyltrifluoroacetone and 1,10-phenanthroline-5,6-dione. Monatsh Chem 145:1913–1917
Melhuish WH (1961). J Phys Chem 65:229235
Gao BJ, Yang YF, Cheng Y, Shi DJ (2002). Spectrosc Spect Anal 22:371–374
Que MD, Ci ZP, Wang YH, Zhu G, Shi YR, Xin SY (2013) Synthesis and luminescent properties of Ca2La8(GeO4)6O2:RE3+ (RE3+=Eu3+, Tb3+, Dy3+, Sm3+, Tm3+) phosphors. J Lumin 144:64–68
Dexter DL (1953) A Theory of Sensitized Luminescence in Solids. J Chem Phys 21:836–850
Sato S, Wada M (1970) Relations between Intramolecular Energy Transfer Efficiencies and Triplet State Energies in Rare Earth β-diketone Chelates. Bull Chem Soc Jpn 43:1955–1962
Yang YT, Zhang SY (2003). Chem J Chin Univ 24:667–670
Sager WF, Filipescu N, Serafin FA (1965) Substituent Effects on Intramolecular Energy Transfer. I. Absorption and Phosphorescence Spectra of Rare Earth β-Diketone Chelates. J Phys Chem 69:1092–1100
Shen CQ, Yan TL, Wang YT, Ye ZJ, Xu CJ, Zhou WJ (2017) Synthesis, structure and luminescence properties of binary and ternary complexes of lanthanide (Eu 3+ , Sm 3+ and Tb 3+ ) with salicylic acid and 1,10-phenanthroline. J Lumin 184:48–54
CIE (1932) Commission internationale de l’ éclairage proceedings, 1931. Cambridge University Press, Cambridge
Malta OL, Brito HF, Menezes JFS, Gonçalves e Silva FR, Alves Jr S, Farias Jr FS, de Andrade AVM (1997) J Lumin 75:255–268
Choppin GR, Peterman DR (1998) Applications of lanthanide luminescence spectroscopy to solution studies of coordination chemistry. Coord Chem Rev 174:283–299
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Authors gratefully acknowledge financial support from the Science and Technology Development Project of Hangzhou City (No.20160432B05).
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Xu, C., Chen, W. & Ding, Y. Facile synthesis and characterization of macromolecular Eu(III) complexes with β-diketone ligands and poly(4-vinyl pyridine-co-methyl methacrylate). J Polym Res 27, 276 (2020). https://doi.org/10.1007/s10965-020-02264-5
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DOI: https://doi.org/10.1007/s10965-020-02264-5