Stereocontrolled Self-Assembly of Ln(III)-Pt(II) Heterometallic Cages with Temperature-Dependent Luminescence

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^III-Pt^II heterometallic cages through coordination-driven self-assembly of enantiopure alkynylplatinum-based metalloligands (L₁, L₂) with lanthanide ions (Ln = Eu^III, Yb^III, Nd^III, Lu^III). 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^III- and Nd^III-containing cages can be extended to the visible region (up to 500 nm). Linear temperature-dependent red and NIR emissions observed on the Ln₄(L₂)₆ (Ln^III = Eu^III and Yb^III, respectively) complexes suggest their potential applications as luminescent temperature sensors, with sensitivities of -0.54% (Ln^III = Eu^III, 77-250 K) and -0.17% (Ln^III = Yb^III, 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.