Chiral lanthanide-silver(I) cluster-based metal-organic frameworks exhibiting solvent stability, and tunable photoluminescence.

Due to the lack of effective synthetic strategies, the preparation of chemically stable chiral Ag(I) cluster-based materials for assembly remains challenging. Here, we have developed an approach to synthesize three pairs of chiral Ln-Ag(I) cluster-based metal-organic frameworks (MOFs) named l-LnAg5-3D (Ln = Gd for 1-L, Eu for 2-L, and Tb for 3-L) and d-LnAg5-3D (Ln = Gd for 1-D, Eu for 2-D, and Tb for 3-D) by employing a chiral Ag(I) cluster ({Ag 5 S 6 }) as the node and Ln 3+ ion as the inorganic linker. Structural analysis revealed that the chiral ligands induced chirality through the entire structure, resulting in a chiral helix arrangement of the C 3 -symmetric chiral {Ag 5 S 6 } nodes and Ln 3+ ions. These compounds showed high solvent stability in various polar organic solvents. The solid-state circular dichroism (CD) spectra of compounds l-LnAg5-3D and d-LnAg5-3D exhibited obvious mirror symmetrical peaks. The emission spectra in the solid state revealed that compound 1-L only exhibited the emission peak of {Ag 5 S 6 }, while compounds 2-L and 3-L exhibited overlapping peaks of Ln 3+ and {Ag 5 S 6 } at different excitation wavelengths. This demonstrates the tunable photoluminescence from {Ag 5 S 6 } to Ln 3+ by introducing different Ln 3+ ions and manipulating the excitation wavelengths. The study underscores the enhanced stability of Ag(I) cluster-based MOFs achieved through the incorporation of Ln 3+ ions and establishes chiral Ln-Ag(I) cluster-based MOFs as promising candidates for advanced materials with tunable photoluminescence.