Petoud Stéphane, Muller Gilles, Moore Evan G, Xu Jide, Sokolnicki Jurek, Riehl James P, Le Uyen N, Cohen Seth M, Raymond Kenneth N
Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Am Chem Soc. 2007 Jan 10;129(1):77-83. doi: 10.1021/ja064902x.
The synthesis, characterization, and luminescent behavior of trivalent Sm, Eu, Dy, and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, g(lum), recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments.
报道了两种对映体、八齿、手性、2-羟基间苯二甲酰胺配体的三价钐、铕、镝和铽配合物的合成、表征及发光行为。这些配合物在溶液中具有高发光性。在手性1-苯乙胺取代基对非手性母体配体进行官能化处理，该取代基位于配合物靠近金属中心的开放面上，得到具有强圆偏振发光（CPL）活性的配合物。这似乎是利用相同配体结构敏化四种不同镧系阳离子并显示CPL活性的系统的首个实例。记录到的铕（III）配合物的发光不对称因子g（lum）是报道的最高值之一，这也是首次证明具有手性配体的钐（III）配合物具有CPL效应。高发光强度与CPL活性的结合应能使大分子在手性环境中实现新的生物分析应用。
