Zhu Qiang-Yu, Zhou Li-Peng, Cai Li-Xuan, Hu Shao-Jun, Li Xiao-Zhen, Sun Qing-Fu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.
Inorg Chem. 2022 Oct 24;61(42):16814-16821. doi: 10.1021/acs.inorgchem.2c02718. Epub 2022 Oct 7.
Structurally well-defined discrete d/f heterometallic complexes show diverse application potential in electrooptic and magnetic materials. However, precise control of the component and topology of such heterometallic compounds with fine-tuned photophysical properties is still challenging. Herein, we report the stereocontrolled syntheses of a series of Ln-Pt heterometallic cages through coordination-driven self-assembly of enantiopure alkynylplatinum-based metalloligands (L, L) with lanthanide ions (Ln = Eu, Yb, Nd, Lu). Taking advantage of the metal-to-ligand charge transfer (MLCT) excited state on the designed alkynylplatinum ligands, the excitation window for the sensitized near-infrared (NIR) luminescence on the Yb- and Nd-containing cages can be extended to the visible region (up to 500 nm). Linear temperature-dependent red and NIR emissions observed on the Ln(L) (Ln = Eu and Yb, respectively) complexes suggest their potential applications as luminescent temperature sensors, with sensitivities of -0.54% (Ln = Eu, 77-250 K) and -0.17% (Ln = Yb, 77-300 K) per K achieved. This work not only offers a good strategy to prepare new d/f heterometallic supramolecular cages but also paves the way for the design of stimuli-responsive luminescent materials.
结构明确的离散d/f异金属配合物在电光和磁性材料中显示出多样的应用潜力。然而，精确控制此类具有微调光物理性质的异金属化合物的组成和拓扑结构仍然具有挑战性。在此，我们报道了通过对映体纯的炔基铂基金属配体（L，L）与镧系离子（Ln = Eu、Yb、Nd、Lu）进行配位驱动的自组装，立体控制合成了一系列Ln-Pt异金属笼。利用设计的炔基铂配体上的金属到配体电荷转移（MLCT）激发态，含Yb和Nd的笼上敏化近红外（NIR）发光的激发窗口可扩展到可见光区域（高达500 nm）。在Ln(L)（Ln分别为Eu和Yb）配合物上观察到的线性温度依赖性红色和近红外发射表明它们作为发光温度传感器的潜在应用，每K的灵敏度分别达到-0.54%（Ln = Eu，77 - 250 K）和-0.17%（Ln = Yb，77 - 300 K）。这项工作不仅为制备新型d/f异金属超分子笼提供了良好策略，也为刺激响应发光材料的设计铺平了道路。
