Department of Chemistry, University of Connecticut, Storrs, Connecticut, 06269, USA.
Department of Chemistry, Vanderbilt University, Nashville, Tennessee, 37235, USA.
Chemistry. 2023 Jun 27;29(36):e202300800. doi: 10.1002/chem.202300800. Epub 2023 May 5.
Strong circularly polarized luminescence (CPL) at 1550 nm is reported for lanthanide complexes supported by Vanol; these are the first examples of coordination of Vanol to lanthanides. A change in the ligand design from a 1,1'-bi-2-naphthol (in Binol) to a 2,2'-bi-1-naphthol (in Vanol) results in significantly improved dissymmetry factors for (Vanol) ErNa (|g |=0.64) at 1550 nm. This is among the highest reported dissymmetry factors to date in the telecom C-band region, and among the highest for any lanthanide complexes. Comparative solid-state structural analysis of (Vanol) ErNa and (Binol) ErNa suggests that a less distorted geometry around the metal center is in part responsible for the high chiroptical metrics of (Vanol) ErNa . This phenomenon was further evidenced in the analogous ytterbium complex (Vanol) YbNa that also exhibit a significantly improved dissymmetry factor (|g |=0.21). This confirms and generalizes the same observation that was made in other visibly emitting, six-coordinate lanthanide complexes. Due to their strong CPL at 1550 nm, the reported complexes are potential candidates for applications in quantum communication technologies. More importantly, our structure-CPL activity relationship study provides guidance towards the generation of even better near-infrared CPL emitters.
报道了镧系配合物在 Vanol 支持下具有强圆偏振发光(CPL)在 1550nm 处;这些是 Vanol 与镧系元素配位的首例实例。配体设计从 1,1'-联-2-萘酚(Binol 中)变为 2,2'-联-1-萘酚(Vanol 中),导致(Vanol)ErNa 在 1550nm 处的不对称因子显著提高(|g|=0.64)。这是迄今为止在电信 C 波段报告的最高不对称因子之一,也是任何镧系配合物中最高的之一。(Vanol)ErNa 和(Binol)ErNa 的比较固态结构分析表明,金属中心周围的几何形状扭曲较小,这在一定程度上导致了(Vanol)ErNa 的高手性度量。这种现象在类似的镱配合物(Vanol)YbNa 中也得到了进一步证实,其不对称因子(|g|=0.21)也显著提高。这证实并推广了在其他可见发射六配位镧系配合物中所做的相同观察结果。由于它们在 1550nm 处具有强 CPL,所报道的配合物是量子通信技术应用的潜在候选物。更重要的是,我们的结构-CPL 活性关系研究为产生更好的近红外 CPL 发射器提供了指导。