Samuel Amanda P S, Lunkley Jamie L, Muller Gilles, Raymond Kenneth N
Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA, ,
Eur J Inorg Chem. 2010 Jul 1;2010(21):3343-3347. doi: 10.1002/ejic.201000309.
Two luminescent terbium(III) complexes have been prepared from chiral ligands containing 2-hydroxyisophthalamide (IAM) antenna chromophores and their non-polarized and circularly-polarized luminescence properties have been studied. These tetradentate ligands, which form 2:1 ligand/Tb(III) complexes, utilize diaminocyclohexane (cyLI) and diphenylethylenediamine (dpenLI) backbones, which we reasoned would impart conformational rigidity and result in Tb(III) complexes that display both large luminescence quantum yield (Φ) values and strong circularly polarized luminescence (CPL) activities. Both Tb(III) complexes are highly emissive, with Φ values of 0.32 (dpenLI-Tb) and 0.60 (cyLI-Tb). Luminescence lifetime measurements in H(2)O and D(2)O indicate that while cyLI-Tb exists as a single species in solution, dpenLI-Tb exists as two species: a monohydrate complex with one H(2)O molecule directly bound to the Tb(III) ion and a complex with no water molecules in the inner coordination sphere. Both cyLI-Tb and dpenLI-Tb display increased CPL activity compared to previously reported Tb(III) complexes made with chiral IAM ligands. The CPL measurements also provide additional confirmation of the presence of a single emissive species in solution in the case of cyLI-Tb, and multiple emissive species in the case of dpenLI-Tb.
由含有2-羟基间苯二甲酰胺(IAM)天线发色团的手性配体制备了两种发光铽(III)配合物,并研究了它们的非偏振和圆偏振发光性质。这些四齿配体形成2:1的配体/Tb(III)配合物,采用二氨基环己烷(cyLI)和二苯乙二胺(dpenLI)骨架,我们认为这将赋予构象刚性,并导致Tb(III)配合物具有大的发光量子产率(Φ)值和强的圆偏振发光(CPL)活性。两种Tb(III)配合物都具有高发射性,Φ值分别为0.32(dpenLI-Tb)和0.60(cyLI-Tb)。在H₂O和D₂O中的发光寿命测量表明,虽然cyLI-Tb在溶液中以单一物种存在,但dpenLI-Tb以两种物种存在:一种是单水合物配合物,其中一个H₂O分子直接与Tb(III)离子结合,另一种是在内层配位球中没有水分子的配合物。与先前报道的用手性IAM配体制备的Tb(III)配合物相比,cyLI-Tb和dpenLI-Tb都表现出增强的CPL活性。CPL测量还进一步证实了cyLI-Tb在溶液中存在单一发射物种,而dpenLI-Tb存在多个发射物种。