Lanthanide Metal-Organic Framework Isomers with Novel Water-Boosting Lanthanide Luminescence Behaviors

Lanthanide metal-organic frameworks (Ln-MOFs) with exceptional optical performance and structural diversity offer a unique platform for the development of luminescent materials. However, Ln-MOFs often suffer from luminescence quenching by high-vibrating oscillators, especially in aqueous solution. Thus, multiple strategies have been adopted to improve the luminescence of Ln³⁺. Anomalous research about water-induced lanthanide luminescence enhancement of Ln-MOFs is in the primary stage. Here, two Eu-based metal-organic framework (Eu-MOF) isomers named QXBA-Eu-1 and QXBA-Eu-2 were constructed by using the same ligand under different solvent thermal conditions, which exhibited distinctive water- and methanol-boosting emission behaviors. As for QXBA-Eu-1, water and methanol molecules replaced the free N,N-dimethylacetamide (DMA) molecules in the framework, repressed the rotation or libration suppression of the QXBA linker, and formed hydrogen bonds with the coordinated water molecules, which suppressed the O-H high-energy vibrations, reduced nonradiative transitions, stabilized the T₁ state, and facilitated the intersystem crossing (ISC) process. For QXBA-Eu-2, water molecules tended to replace the coordinated DMA ligands, which altered the S₁ and T₁ energy levels of the ligand and facilitated the ligand-to-metal energy transfer (LMET) process and strengthened the luminescence of Eu³⁺. Importantly, free solvent molecules and the hydroxylation of Eu³⁺ centers also restrained the rotation or libration of the QXBA linker, by which the nonradiative transition was further inhibited and the lanthanide luminescence enhanced. Thus, this work not only opened an unprecedented path to enhance lanthanide luminescence in aqueous solution but also expanded its application scope.