Jean-Claude Bunzli - Tuning the decay time of lanthanide-based near infrared luminescence from micro- to milliseconds through d -> f energy transfer in discrete heterobimetallic complexes

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      Torelli,S., Imbert,D., Cantuel,M., Bernardinelli,G., Delahaye,S.,   Hauser,A., Bunzli,J.C.G., Piguet,C. Chemistry-A European   Journal 2005 11 (11) 3228-3242

      Abstract: Inert and optically active   pseudo-octahedral (CrN6)-N-III and (RuN6)-N-II chromophores have   been incorporated by self-assembly into heterobimetallic   triple-stranded helicates HHH-[CrLnL(3)](6+) and   HHH-[RuLnL(3)](5+). The crystal structures of   [CrLnL(3)](CF3SO3)(6) (Ln = Nd, Eu, Yb, Lu) and [RuLn(3)]-   (CF3SO3)(5) (Ln = Eu, Lu) demonstrate that the helical structure   can accommodate metal ions of different sizes, without sizeable   change in the intermetallic M(...)Ln distances. These systems are   ideally suited for unravelling the molecular factors affecting   the intermetallic nd -> 4f communication. Visible irradiation   of the (CrN6)-N-III and (RuN6)-N-III chromophores in   HHH-[MLnL(3)](5/6+) (Ln = Nd, Yb, Er; M = Cr, Ru) eventually   produces lanthanide-based near infrared (NIR) emission, after   directional energy migration within the complexes. Depending on   the kinetic regime associated with each specific d-f pair, the   NIR luminescence decay times can be tuned from micro- to   milliseconds. The origin of this effect, together with its   rational control for programming optical functions in discrete   heterobimetallic entities, are discussed

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