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  4. Remarkable Tuning of the Photophysical Properties of Bifunctional Lanthanide tris(Dipicolinates) and its Consequence on the Design of Bioprobes
 
research article

Remarkable Tuning of the Photophysical Properties of Bifunctional Lanthanide tris(Dipicolinates) and its Consequence on the Design of Bioprobes

Gassner, Anne-Laure
•
Duhot, Céline
•
Bünzli, Jean-Claude G.  
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2008
Inorganic Chemistry

Derivatives of dipicolinic acid with a polyoxyethylene pendant arm at the pyridine 4-position have been functionalized for potential grafting with biological material. Four ligands with different terminal functions (alcohol, methoxy, phtalimide and amine) have been synthesized, which react with trivalent lanthanide ions $Ln^{III}$ to yield triple helical $[Ln(L)3]^{3-}$ complexes, as shown by NMR and UV-vis titrations. The tris chelates display large thermodynamic stability with $log \beta{13} \approx 19-20$ for all $Eu^{III}$ complexes for instance. Photophysical measurements reveal adequate sensitization of the metal-centered luminescence in the europium ($\eta_{sens} = 33-72%$) and terbium complexes, which is modulated by the nature of the terminal function. The lifetimes of the metal-centered excited states are long, up to 1.4 ms for $[Eu(L)_3]^{3-}$ and 1.6 ms for $[Tb(L)_3]^{3-}$ at room temperature, in line with hydration numbers essentially equal to zero. Quantum yields are as high as 29% for the $[Eu(L^{NH2})_3]^{3-}$ and 18% for the $[Tb(L^{OH})_3]^{3-}$ tris chelates in water at physiological pH. These series of complexes demonstrate the extent of fine-tuning achievable for lanthanide luminescent probes and are simple models for investigating the effect of binding to biological molecules on the metal-centered luminescent properties.

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Type
research article
DOI
10.1021/ic800842f
Web of Science ID

WOS:000258709500046

Author(s)
Gassner, Anne-Laure
Duhot, Céline
Bünzli, Jean-Claude G.  
Chauvin, Anne-Sophie  
Date Issued

2008

Published in
Inorganic Chemistry
Volume

47

Start page

7802

End page

7812

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCSL  
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/27928
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