Jean-Claude Bunzli - Multiphoton-Excited Luminescent Lanthanide Bioprobes: Two- and Three-Photon Cross Sections of Dipicolinate Derivatives and Binuclear Helicates

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      Eliseeva,S.V., Aubock,G., van Mourik,F., Cannizzo,A., Song,B.,   Deiters,E., Chauvin,A.S., Chergui,M., Bunzli,J.C.G. Journal   of Physical Chemistry B 2010 114  (8) 2932-2937

      Abstract: Multiphoton excited luminescent   properties or water-soluble Eu(III) and Tb(III) complexes with   derivatives of dipicolinic acid functionalized with a   polyoxyethylene pendant arm and terminal groups,   [Eu(L(OMe))(3)](3-), [Eu(L(NH2))(3)](3-), and [Tb(L(OH))(3)](3-),   as well as of binuclear helicates with overall composition   [Ln(2)(L(CX))(3)] (X = 2, 5) are investigated. Characteristic   emission from the (5)D(0) and (5)D(4) excited levels of Eu(III)   and Tb(III), respectively, upon approximate to 800 nm excitation   results from three-photon absorption (3PA) for   [Eu(L(OMe))(3)](3-), [Eu(L(NH2))(3)](3-), [Tb(L(OH))(3)](3-), and   [Ln(2)(L(C2))(3)], while luminescence from [Eu(2)(L(C5))(3)] is   induced by two-photon absorption (2PA) owing to its IPA spectrum   extending further into the visible. The 3PA cross sections have   been determined and are the first ones reported for lanthanide   complexes: (i) those of Eu(III) and Tb(III) bimetallic helicates   [Ln(2)(L(C2))(3)] are 20 times larger compared to the   corresponding values for tris(dipicolinates); (ii) derivatization   of dipicolinic acid for Tb(III) complexes has almost no influence   on the 3PA cross section; however, for Eu(III) complexes a   similar to 2 times decrease is observed. The feasibility of   [Eu(2)(L(C5))(3)] its multiphoton luminescence bioprobe is   demonstrated by two-photon scanning microscopy imaging   experiments on HeLa cells incubated with this bimetallic helicate

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