Ruggieri Silvia, Willis Oliver George, Mizzoni Silvia, Cavalli Enrico, Sanadar Martina, Melchior Andrea, Zinna Francesco, Di Bari Lorenzo, Bisag Giorgiana Denisa, Fochi Mariafrancesca, Bernardi Luca, Piccinelli Fabio
Luminescent Materials Laboratory, DB, University of Verona, and INSTM, UdR Verona, Verona 37134, Italy.
Department of Chemistry and Industrial Chemistry, University of Pisa, Pisa 56124, Italy.
Inorg Chem. 2025 Mar 24;64(11):5505-5512. doi: 10.1021/acs.inorgchem.4c05420. Epub 2025 Mar 12.
In this contribution, we present new NIR-CPL/CD active Yb(III) complexes, which are synthesized by combining two ligands characterized by different types of chirality: central and axial chirality. The ligand bearing central chirality is represented by the neutral -,'-bis(2-pyridylmethylidene)-1,2-(, or ,) cyclohexanediamine (), whereas the axial ligand is 1,1'-binaphthyl-2,2'-diol (BINOL-H). A combined H NMR, thermodynamic (spectrophotometric titrations), and theoretical (DFT structural calculations) study is presented, revealing the high stability in the methanol solution of the homochiral -symmetric anionic [Yb(BINOL)] complexes, in which the two labile BINOLate molecules exhibit the same stereochemistry ( or ). The metal ion-related optical and chiroptical properties of the complexes in the near-infrared spectral region are here presented and discussed: while the axial chirality dominates the circularly polarized luminescence features, the NIR-CD signal is affected by both chiral elements.
在本论文中，我们展示了新型近红外圆偏振发光/圆二色性（NIR-CPL/CD）活性的Yb(III)配合物，它们是通过将两种具有不同手性类型（中心手性和轴手性）的配体结合而合成的。具有中心手性的配体由中性的-,'-双(2-吡啶基亚甲基)-1,2-(,或,)环己二胺（）表示，而轴手性配体是1,1'-联萘-2,2'-二醇（BINOL-H）。本文进行了结合氢核磁共振（H NMR）、热力学（分光光度滴定）和理论（密度泛函理论结构计算）的研究，揭示了同手性-对称阴离子型[Yb(BINOL)]配合物在甲醇溶液中的高稳定性，其中两个不稳定的双萘酚盐分子表现出相同的立体化学结构（或）。本文展示并讨论了配合物在近红外光谱区域中与金属离子相关的光学和手性光学性质：虽然轴手性主导圆偏振发光特征，但近红外圆二色性信号受两种手性元素的影响。
