000171383 001__ 171383
000171383 005__ 20181203022532.0
000171383 0247_ $$2doi$$a10.1021/ic200450x
000171383 02470 $$2ISI$$a000290978400054
000171383 037__ $$aARTICLE
000171383 245__ $$aDeciphering Three Beneficial Effects of 2,2 '-Bipyridine-N,N '-Dioxide on the Luminescence Sensitization of Lanthanide(III) Hexafluoroacetylacetonate Ternary Complexes
000171383 269__ $$a2011
000171383 260__ $$c2011
000171383 336__ $$aJournal Articles
000171383 520__ $$aLanthanide hexafluoroacetylacetonate ternary complexes with 2,2'-bipyridine-N,N'-dioxide, [Ln(hfa)(3)(bpyO2)], were synthesized for Ln = Eu, Gd, Tb, and Lu and fully characterized by elemental, thermal, and mass-spectrometric analyses. The X-ray crystal structure of [Eu(hfa)(3)(bpyO2)] center dot 0.5C(6)H(6) reveals an octa-coordinate metal ion lying in a severely distorted trigonal dodecahedron geometry; the Eu-O distances lie in the range 2.36-2.44 angstrom with no significant difference between hfa and bpyO2. angstrom detailed comparative photophysical investigation has been carried out to determine the exact influence of the introduction of bpyO2 in the inner coordination sphere of the metal ion in replacement of the two water molecules in [Ln(hfa)(3)(H2O)(2)]center dot While this replacement is detrimental for Tb, it leads to a 15-fold increase in the overall quantum yield for Eu. This large improvement originates from (i) a better sensitization efficiency, the ancillary ligand being responsible for 3/4 of the energy transfer, (ii) elimination of nonradiative deactivation pathways through'harmonics of O-H vibrations, and (iii) reduction in the radiative lifetime. The latter influence is rarely documented, but it accounts here for a approximate to 25% increase in the intrinsic quantum yield, so that more attention should be given to this parameter when designing highly luminescent lanthanide complexes.
000171383 6531_ $$aEmission Quantum Yield
000171383 6531_ $$aStructural Features
000171383 6531_ $$aRadiative Lifetime
000171383 6531_ $$aCrystal-Structure
000171383 6531_ $$aEnergy-Transfer
000171383 6531_ $$aCoordination
000171383 6531_ $$aChromophores
000171383 6531_ $$aBipyridine
000171383 6531_ $$aLigands
000171383 6531_ $$aPhotoluminescence
000171383 700__ $$0241991$$aEliseeva, Svetlana V.$$g188686
000171383 700__ $$aPleshkov, Dmitry N.
000171383 700__ $$aLyssenko, Konstantin A.
000171383 700__ $$aLepnev, Leonid S.
000171383 700__ $$0241990$$aBunzli, Jean-Claude G.$$g122803
000171383 700__ $$aKuzmina, Natalia P.
000171383 773__ $$j50$$q5137-5144$$tInorganic Chemistry
000171383 909C0 $$0252081$$pLCSL$$xU10099
000171383 909CO $$ooai:infoscience.tind.io:171383$$pSB$$particle
000171383 917Z8 $$x206725
000171383 937__ $$aEPFL-ARTICLE-171383
000171383 973__ $$aEPFL$$rREVIEWED$$sPUBLISHED
000171383 980__ $$aARTICLE