Feng Tingting, Cai Rui, Zhu Zhenhua, Zhou Quan, Sickinger Annika, Maury Olivier, Guyot Yannick, Bensalah-Ledoux Amina, Guy Stéphan, Baguenard Bruno, Le Guennic Boris, Tang Jinkui
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, P. R. China.
Chemistry. 2025 Jun 23;31(35):e202500910. doi: 10.1002/chem.202500910. Epub 2025 May 29.
Chiral lanthanide complexes hold great potential in developing advanced circularly polarized luminescence (CPL) materials in the near-infrared (NIR) wavelength range. While various ligands, such as β-diketonates and biphenols, have been successfully used to sensitize NIR emission of lanthanide ions, little attention has been paid to regulating CPL behaviors via ligand modification. In this study, we report the synthesis, structure, luminescence, and chiroptical properties of a pair of novel air-stable Shibasaki-type Yb(III) enantiomers supported by 3,3'-fluorinated binaphthol (FBINOL). Compared to their nonfluorinated counterparts, these fluorinated complexes exhibit larger dihedral angles between the two naphthyl moieties and more distorted octahedral coordination environments around the Yb(III) ion, leading to increased overall crystal field splitting. These structural modifications result in enhanced photophysical properties: the luminescence lifetime (τ), sensitization efficiency (η), and quantum yield (QY) improve from 2.1 µs, 38%, and 0.7% to 2.7 µs, 63%, and 1.8%, respectively. Additionally, the dissymmetry factor (g) and CPL brightness (B) at 963 nm increase by 32% and one order of magnitude, respectively. The scope of such chemical modification is broad, potentially encompassing a variety of BINOL derivatives, offering a unique platform to further elucidate the relationship between structural and electronic properties and CPL activity in lanthanide systems.
手性镧系配合物在开发近红外（NIR）波长范围内的先进圆偏振发光（CPL）材料方面具有巨大潜力。虽然各种配体，如β-二酮和联苯酚，已成功用于敏化镧系离子的近红外发射，但通过配体修饰来调节CPL行为却很少受到关注。在本研究中，我们报道了一对由3,3'-氟化联萘酚（FBINOL）支撑的新型空气稳定的柴崎型Yb(III)对映体的合成、结构、发光和手性光学性质。与它们的非氟化对应物相比，这些氟化配合物在两个萘基部分之间表现出更大的二面角，并且在Yb(III)离子周围具有更扭曲的八面体配位环境，导致整体晶体场分裂增加。这些结构修饰导致光物理性质增强：发光寿命（τ）、敏化效率（η）和量子产率（QY）分别从2.1 μs、38%和0.7%提高到2.7 μs、63%和1.8%。此外，963 nm处的不对称因子（g）和CPL亮度（B）分别增加了32%和一个数量级。这种化学修饰的范围很广，可能涵盖各种BINOL衍生物，为进一步阐明镧系体系中结构和电子性质与CPL活性之间的关系提供了一个独特的平台。
