Department of Inorganic and Analytical Chemistry, University of Geneva, quai E. Ansermet 30, 1211, Geneva 4, Switzerland.
Department of Organic Chemistry, University of Granada, Unidad de Excelencia de Química (UEQ), Avda. Fuentenueva, 18071, Granada, Spain.
Angew Chem Int Ed Engl. 2021 Apr 26;60(18):10095-10102. doi: 10.1002/anie.202101158. Epub 2021 Mar 11.
A series of highly emissive inert and chiral Cr complexes displaying dual circularly polarized luminescence (CPL) within the NIR region have been prepared and characterized. The helical [Cr(dqpR) ] (dqp=2,6-di(quinolin-8-yl)pyridine; R=OCH , Br or C≡CH) complexes were synthesized as racemic mixtures and resolved into their respective PP and MM enantiomers by chiral stationary phase HPLC. The corresponding enantiomers show large g ≈0.2 and high quantum yield of up to 17 %, which afford important CPL brightness of up to 170 m cm , a key point for applications as chiral luminescent probes. Moreover, the long-lived CP-NIR emission provided by these chromophores (ms range) in aqueous solution opens the way toward the quantification of chiral targets in biological systems with time-gated detection. Thus, such chiral chromophores based on earth abundant and inert 3d metals open new perspectives in the field of CPL and represent an alternative to precious 4d, 5d and to labile 4f metal-based complexes.
已经制备并表征了一系列具有高发光效率的惰性手性 Cr 配合物,它们在近红外区域内显示出双圆偏振发光 (CPL)。手性 [Cr(dqpR)](dqp=2,6-二(8-喹啉基)吡啶;R=OCH3、Br 或 C≡CH)配合物作为外消旋混合物合成,并通过手性固定相 HPLC 分离成各自的 PP 和 MM 对映异构体。相应的对映异构体表现出较大的 g 值 ≈0.2 和高达 17%的高量子产率,这提供了高达 170 m cm 的重要 CPL 亮度,这是作为手性发光探针应用的关键。此外,这些发色团在水溶液中提供的长寿命 CP-NIR 发射(毫秒范围)为利用时间门控检测在生物系统中定量手性靶标开辟了道路。因此,基于地球丰富且惰性的 3d 金属的这种手性发色团在 CPL 领域开辟了新的前景,并代表了对贵金属 4d、5d 和不稳定的 4f 金属基配合物的替代。