Microporous Metal–Organic Frameworks Based on Zinc Clusters and Their Fluorescence Enhancements towards Acetone and Chloroform

Two microporous metal–organic frameworks (MOFs) based on zinc clusters, that is, [Zn 3 (BDC) 2 (HBDC) 2 ] · 2DMA · 4CH 3 OH · 2H 2 O ( 1 ; H 2 BDC = 1,4‐dicarboxybenzene, DMA = N , N ‐dimethylacetamide) and [(CH 3 ) 2 NH 2 ] 2 [Zn 7 (µ 4 ‐O) 2 (NDC) 6 ] · DMF · H 2 O ( 2 ; H 2 NDC = 1,4‐naphthalenedicarboxylic acid, DMF = N , N ‐dimethylformamide), were synthesized by a solvothermal method. Both compounds possess three‐dimensional porous skeletons with square channels and exhibit interesting blue fluorescence. Compound 1 consists of trinuclear Zn II building units bridged by both BDC 2– and HBDC – ligands, which results in the formation of a 2,8‐connnected topological net (hex). Compound 2 features another 2,8‐connected topological net (bcu) that is constructed by eight‐connected Zn 7 (µ 4 ‐O) 2 clusters and two‐connected NDC 2– ligands. The solid‐state and solvent‐dependent fluorescence of the two MOFs revealed that 1 and 2 showed fluorescence enhancement effects in the presence of acetone and chloroform, respectively, which thereby demonstrates their potential as fluorescent sensors for selective sensing towards acetone and chloroform.