SCSC Transformation and Post-Synthesis Modification of MOFs with Proton Conduction and Ratiometric...

The modification of metal-organic framework (MOF) materials to facilitate their practical applications is an extremely challenging and meaningful topic. In this work, two stepwise modification strategies for MOFs were conducted. First, we have demonstrated a single-crystal-to-single-crystal (SCSC) transformation from a microporous three-dimensional (3D) MOF to a two-dimensional (2D) coordination polymer (CP). The centrosymmetric [Cd(3-bpdb)(MeO-ip)] (1) transforms into a chiral [Cd₂(3-bpdb)(MeO-ip)₂(CH₃OH)₂] (2), which is triggered by the reaction time with methanol that acts as a structure-directing agent. The conversion relationship of 1 to 2 at different reaction times was studied in detail. Density functional theory (DFT) calculations clearly state that the irreversible formation of 2 is thermodynamically favorable. Intriguingly, 2 exhibits good proton conduction of 1.34 × 10^-3 S cm^-1 under 363 K and 98% relative humidity (RH) due to unique H-bond network characteristics. To the best of our knowledge, there are very few cases of 3D to 2D SCSC transformation stimulated by reaction time. The results have important implications for understanding the SCSC transformation mechanism and synthetic chemistry. On the other hand, the lanthanide³⁺-functionalized hybrids (Ln³⁺-MOF), Ln³⁺@1, were continuously prepared by incorporating luminescent Ln³⁺ ions into the structure of 1 through encapsulating post-synthesis modification (PSM). Tb³⁺@1 exhibits double emission in water and shows visual ratiometric fluorescence behavior for sensing glutamic acid (Glu), tryptophan (Trp), and Al³⁺, which is more reliable and accurate than single emission. Our work may not only provide new insights into the multiple modification of MOF materials but also promote the practical application of such materials.