A new tridentate organic ligand, 4-(4-carbazol-9-yl-butoxy)-pyridine-2,6-dicarboxylic acid (H2CBODPA), has been designed and synthesized. The orresponding europium and terbium complexes, Na3Eu(CBODPA)3 and Na3Tb(CBODPA)3, have also been synthesized. The effective excitation wavelengths of the two complexes shifted significantly to longer wavelengths by configuration of the organic ligand’s structure, the effective excitation wavelengths shifted about 70 nm to longer wavelengths compared with those of the europium and terbium complexes with pyridine-2,6-dicarboxy acid as a ligand. Characteristic red emissions of europium ions and green emissions of terbium ions were obtained from dilute Na3Eu(CBODPA)3and Na3Tb CBODPA)3 solutions under near ultraviolet radiations at around 350 nm. The results may provide a theoretical basis to the design and synthesis of organic rare earth luminescent bioprobes with longer excitation wavelengths.
AN Bao-li, HUANG Xiao-di, MA Li-hua, XU Jia-qiang
. Synthesis and Photoluminescence Properties of Two Organic Europium (Ⅲ) and Terbium (Ⅲ) Complexes[J]. Journal of Shanghai University, 2013
, 19(1)
: 90
-94
.
DOI: 10.3969/j.issn.1007-2861.2013.01.018
[1] Weissman S I. Intramolecular energy transfer the fluorescence of complexes of europium [J]. J Chem Phys, 1942, 10(4): 214-217.
[2] Tremblay M S, Halim M, Sames D. Cocktails of Tb3+ and Eu3+ complexes: A general platform for the design of ratiometric optical probes [J]. J Am Chem Soc, 2007,
129(24): 7570-7577.
[3] Nonat A M, Quinn S J, Gunnlaugsson T. Mixed f − d coordination complexes as dual visible-and nearinfrared-emitting probes for targeting DNA [J]. Inorg Chem, 2009, 48(11): 4646-4648.
[4] Rajapakse H E, Reddy D R, Mohandessi S, et al. Luminescent terbium protein labels for time-resolved microscopy and screening [J]. Angew Chem, 2009, 121(27): 5090-5092.
[5] Bunzli J C G. Lanthanide luminescence for biomedical analyses and imaging [J]. Chem Rev, 2010, 110(5): 2729-2755.
[6] An B L, Ye J Q, Gong M L, et al. Luminescence and thermal stability of tris (pyridine dicarboxyate) terbate(Ⅲ) complex incorporated in silica matrix by sol-gel method [J]. Mater Res Bull, 2001, 36(7/8): 1335-1346.
[7] An B L, Liu P Y, Shi J X, et al. Preparation, photoluminescence and thermal stability of sodium tris(pyridine dicarboxylato) europate(Ⅲ) complex incorporated into
silica matrix [J]. J Mater Sci-Mater El, 2003, 14(3): 125-128.
[8] Gy¨orgy H, Cristian R, Zolt´ah K¨ont¨os, et al. A new efficient method for the preparation of 2, 6-pyridinedihiethyl ditosylates from dimethyl 2, 6-pyridinedicarboxylates [J]. Syn Commun, 1999, 29(21): 3719-3731.
[9] Prasad T, Timothy F, Derek P, et al. Investigating carbazole jacketed precursor dendrimers: sonochemical synthesis, characterization, and electrochemical crosslinking properties [J]. J Am Chem Soc, 2007, 129(41): 12537-12548.
[10] Ren Y Y, An B L, Xu Q. Strong luminescence of novel water-soluble lanthanide complexes sensitized by pyridine-2,4,6-tricarboxylic acid [J]. J Alloys Compd, 2010, 501(1): 42–46.
[11] An B L, Zhang N, Cheah K W, et al. High yield luminescence of a novel europium complex by excimer excitation and f−f absorption of Eu3+ [J]. J Alloys Compd,
2008, 458(1/2): 457-461.
[12] An B L, Gong M L, Cheah K W, et al. Synthesis, structure and photoluminescence of novel lanthanide (Tb(Ⅲ), Gd(Ⅲ)) complexes with 6-diphenylamine carbonyl
2-pyridine carboxylate [J]. J Alloys Compd, 2004, 368(1/2): 326-332.
[13] Crosby G A, Whan R E, Alire R M. Intramolecular energy transfer in rare earth chelates. Role of the triplet state [J]. J Chem Phys, 1961, 34(3): 743-748.
[14] Sabbatinin, Guardigli M, Lehn J M. Luminescent lanthanide complexes as photochemical supermolecular devices [J]. Coord Chem Rev, 1993, 123(1/2): 201-228.
[15] Dexter D L. A theory of sensitized luminescence in solids [J]. J Chem Phys, 1953, 21(5): 836-850.
[16] Dean C R S, Shepherd T M. Evaluation of the intramolecular energy transfer rate constants in crystalline Eu(hfaa)4ButNH3 [J]. J Chem Soc Faraday Trans 2, 1975, 71(1): 146-155.
