Department of Chemistry, Ångström Laboratory, Uppsala University, Box 523, 75120, Uppsala, Sweden.
Dalton Trans. 2018 Aug 21;47(31):10702-10714. doi: 10.1039/c8dt01270a. Epub 2018 Jun 20.
Carbostyrils are among the most widely used sensitising antennae for luminescent lanthanides; they afford bright complexes with Eu and Tb, and can also sensitise the emissions of the less commonly used Sm, Dy, Yb and Nd. Systematic studies on the effect of structural variations on the photophysical properties and lanthanide sensitising abilities of carbostyrils can therefore have a large impact. We replaced the secondary amide linker that connects the metal binding site to the antenna with a carboxymethyl-substituted tertiary amide. Eight Tb and Eu complexes were prepared. All had higher lanthanide luminescence quantum yields (Φ) than their secondary amide analogues; three Tb emitters had Φ > 40%. Eu complexes had Φ up to 11.6%. The antenna singlet and triplet excited states are slightly shifted, while the metal coordination sphere is unchanged by the introduction of the carboxymethyl group.
碳氮杂环丁烷是最广泛应用的敏化剂之一,用于镧系元素的发光;它们提供了 Eu 和 Tb 的亮复合物,并且还可以敏化较少使用的 Sm、Dy、Yb 和 Nd 的发射。因此,对碳氮杂环丁烷结构变化对光物理性质和镧系元素敏化能力的影响进行系统研究,可以产生重大影响。我们用羧甲基取代的叔酰胺取代了将金属结合位点连接到天线的二级酰胺连接体。制备了 8 个 Tb 和 Eu 配合物。所有配合物的镧系元素荧光量子产率(Φ)都高于它们的二级酰胺类似物;三个 Tb 发射器的Φ>40%。Eu 配合物的Φ高达 11.6%。引入羧甲基基团后,天线单重态和三重态激发态略有移动,而金属配位球不变。