Herein we systematically investigated the coordination assembly behavior of Zr4L6 cages with Eu3+ ions at room temperature. Through adjustment of the concentration of Eu salt and changes of the type and molar ratio of the solvent, a series of Zr4L6-Eu structures with different structure dimensionalities have been synthesized and structurally characterized. In addition, we also studied the optical properties of these materials in detail, including the fluorescent and third-order nonlinear-optical properties. Most notably, a 2D layer structure with a strong aromatic π···π-stacking force exhibits a good optical-limiting effect.

Comprehensive Summary Herein, we demonstrate a very useful strategy to construct cage‐based metal‐organic frameworks (MOFs) with third‐order nonlinear‐optical properties. More specifically, by employing the Zr4L6 (L = embonate) cages to assembly with N‐contained ligands and Mn2+/Zn2+ ions, four Zr4L6‐cage‐based MOFs have been synthesized and structurally characterized. Among them, a 3D framework with strong aromatic π − π stacking force exhibits a good optical limiting effect.