Porous architectures are generally important for chiral metal–organic frameworks (MOFs) to fulfill chiroptical properties of guests, while induced chirality of guest molecules by nonporous chiral MOFs remains rare. Herein, we demonstrate a case of applying a cocrystallization strategy to construct circularly polarized luminescence (CPL)-active host (nonporous MOFs)-guest hybrid systems. A pair of novel nonporous enantiomeric MOFs (L/D-CdMOF), are hydrothermally synthesized as chiral templates, exhibiting blue emission and chiroptical properties. By cocrystallization with achiral rhodamine 6G (R6G) through dye doping method, a pair of chiral assemblies (L/D-CdMOF $\supset$R6G adducts) are obtained, showing bluish-white CPL with good g_lum values at the 10⁻³ level. Leveraging the processability of these cocrystallization-engineered hybrids, a bluish-white CPL-emitting diode is fabricated, and CPL-active inks are developed. These inks are used in photo-curing three-dimensional (3D) printing to create various chiral adduct-based agglomerates with bluish-white CPL, demonstrating multidimensional chirality engineering via additive manufacturing. This work offers a creative avenue for the development of bluish-white CPL materials and provides insights for advanced applications.

In this study, an alkynyl-modified aromatic dicarboxylic acid bifunctional ligand was selected to construct lanthanide compound {[Eu₄(ebdc)₆(4,4-bpy)_0.5(H₂O)_4.5]·(C₂H₅OH)_1.25(H₂O)}_n (Eu-MOF, H₂ebdc = 5-ethynyl-isophthalic acid, 4,4-bpy = 4,4-bipyridine, and MOF = metal-organic framework), of which the uncoordinated alkynyl group would be used to anchor silver nanoclusters (Ag NCs). The Eu-MOF exhibits double emission peaks, located at 492 and 611 nm, respectively, in which the high-energy blue emission is associated with alkynyl-modified ligand while the low-energy red emission belongs to characteristic emission of Eu³⁺, indicating that ligands can effectively sensitize Eu³⁺ luminescence. The intensity ratio of the dual emission fluorescence peaks of Eu-MOF displays a good linear relationship with temperature, which realizes the detection function in the low temperature region of 75–275 K, and the thermal sensitivity reaches 1.5398%·K⁻¹. After anchoring the Ag NCs, the high-energy blue emission is significantly quenched, indicating that the Ag NCs are indeed confined into the framework and interact with the alkynyl group, and thus change the overall electronic distribution. This is the first case of anchoring Ag NCs by a luminescent Eu-MOF and studying nanocluster loading by using spectroscopic properties. In addition, the Ag NCs@Eu-MOF also shows a good catalytic activity for cycloaddition reaction from CO₂ and epoxides. This study not only provides ideas for exploring the changes in optical properties of luminescent MOFs and Ag NCs caused by confinement effect, but also expands their potential applications in various fields.