Europium Complexes of Tris(dipicolinato) Derivatives Coupled to Methylumbelliferone: A Double Sensitization

被引:23
作者
Andres, Julien [1 ]
Chauvin, Anne-Sophie [1 ]
机构
[1] Ecole Polytech Fed Lausanne, ISIC, CH-1015 Lausanne, Switzerland
基金
瑞士国家科学基金会;
关键词
N; O ligands; Lanthanides; Luminescence; Europium; Sensitization; LANTHANIDE COMPLEXES; OPTICAL SPECTROSCOPY; AQUEOUS-SOLUTIONS; LUMINESCENCE; ACID; CRYSTAL; LIGANDS; TERBIUM; TRANSITION; MICROSCOPY;
D O I
10.1002/ejic.201000126
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A para-poly(oxyethylene) dipicolinic acid derivative coupled to methylumbelliferone was synthesized and used as a ligand for coordination with europium ions. Characterization of the complex by mass spectrometry and spectrophotometry was performed in aqueous solution and points to the formation of the 1:3 Eu/L complex. Physicochemical properties are close to those of already reported dipicolinato complexes, confirming that the presence of a coumarin chromophore does not interfere with complex formation. Photophysical measurements result in observed lifetimes of 1.4 ms and intrinsic quantum yields, Phi(Eu)(Eu), ranging from 33 to 50% (depending on the solvent used). Selective excitation can be performed either mostly on the dipicolinate (DPA) backbone (at 280 nm) or exclusively on the coupled coumarin chromophore in the near visible range (320 nm). Despite the spatial distance between the antenna and the lanthanide ion, europium emission was observed upon 320 nm excitation together with the coumarin emission. The different sensitization pathways have been explored and rationalized. Finally, the complex has been used to probe the ratio of a binary mixture of solvent, establishing the potential interest of this new class of ligands in many fields of research, from photophysics to applied chemistry.
引用
收藏
页码:2700 / 2713
页数:14
相关论文
共 48 条
[1]   Intrinsic quantum yields and radiative lifetimes of lanthanide tris(dipicolinates) [J].
Aebischer, Annina ;
Gumy, Frederic ;
Buenzli, Jean-Claude G. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2009, 11 (09) :1346-1353
[2]   SIMPLE, ONE-STEP FLUOROMETRIC METHOD FOR DETERMINATION OF NANOMOLAR CONCENTRATIONS OF TERBIUM [J].
BARELA, TD ;
SHERRY, AD .
ANALYTICAL BIOCHEMISTRY, 1976, 71 (02) :351-357
[3]   Lanthanide-Based Luminescent Hybrid Materials [J].
Binnemans, Koen .
CHEMICAL REVIEWS, 2009, 109 (09) :4283-4374
[4]   A STRONGLY LUMINESCENT ORGANIC-SOLVENT-SOLUBLE SALT OF THE TRIS(DIPICOLINATO)EUROPIUM(III) TRIANION [J].
BRAYSHAW, PA ;
HARROWFIELD, JM ;
SOBOLEV, AN .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1995, 51 :1799-1802
[5]   SYNTHETIC, STRUCTURAL, AND SPECTROSCOPIC STUDIES ON SOLIDS CONTAINING TRIS(DIPICOLINATO) RARE-EARTH ANIONS AND TRANSITION OR MAIN-GROUP METAL-CATIONS [J].
BRAYSHAW, PA ;
BUNZLI, JCG ;
FROIDEVAUX, P ;
HARROWFIELD, JM ;
KIM, Y ;
SOBOLEV, AN .
INORGANIC CHEMISTRY, 1995, 34 (08) :2068-2076
[6]   Bacterial spore detection by [Tb3+(macrocycle)(dipicolinate)] luminescence [J].
Cable, Morgan L. ;
Kirby, James P. ;
Sorasaenee, Karn ;
Gray, Harry B. ;
Ponce, Adrian .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (06) :1474-1475
[7]  
CAPPELLI A, 2008, Patent No. 2007059698
[8]   A versatile ditopic ligand system for sensitizing the luminescence of bimetallic lanthanide bio-imaging probes [J].
Chauvin, Anne-Sophie ;
Comby, Steve ;
Song, Bo ;
Vandevyver, Cairoflne D. B. ;
Buenzli, Jean-Claude G. .
CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (06) :1726-1739
[9]   Europium and terbium tris (dipicolinates) as secondary standards for quantum yield determination (vol 40, pg 193, 2007) [J].
Chauvin, Anne-Sophie ;
Gumy, Frederic ;
Imbert, Daniel ;
Bunzli, Jean-Claude G. .
SPECTROSCOPY LETTERS, 2007, 40 (01) :193-193
[10]   Two-photon microscopy and spectroscopy of lanthanide bioprobes [J].
D'Aleo, Anthony ;
Pompidor, Guillaume ;
Elena, Benedicte ;
Vicat, Jean ;
Baldeck, Patrice L. ;
Toupet, Loic ;
Kahn, Richard ;
Andraud, Chantal ;
Maury, Olivier .
CHEMPHYSCHEM, 2007, 8 (14) :2125-2132