Insight understanding into influence of binding mode of carboxylate with metal ion on ligand-centered luminescence properties in Pb-based coordination polymers

Two Pb-based coordination polymers emit room temperature ligand-centered phosphorescence with high quantum yield, which color is strongly dependent on the binding mode of carboxylate with Pb2+ ion. [Display omitted] In the crystal engineering area, it is important to clearly demonstrating the relationship of structure and certain functionality. Herein, we present the study of the relationship of structure with phosphorescent nature for two new room temperature phosphorescence (RTP) coordination polymers (CPs). [Pb(FDA)(H2O)] (1) and [NH3(CH3)NH2(CH3)2][Pb4(FDA)5] (2), where H2FDA is 2,5-furandicarboxylic acid, have been synthesized by solvothermal method using different solvents and Pb2+ sources and characterized by microanalysis, powder X-ray diffraction (PXRD), thermogravimetric (TG), IR and UV–vis spectra. The Pb2+ ions adopt bicapped triangle prism coordination sphere in 1 and 2, which are connected together via FDA2− ligands into bilayer structure in 1 while pillared-layer framework in 2. The FDA2− ligands show different bridging modes in 1 and 2, leading to distinct coordination interactions between Pb2+ ion and FDA2− ligand in both CPs. Both 1 and 2 emit ligand-centered RTP due to the heavy atom of Pb2+ ion, with a lifetime and quantum yield of 0.62 ms and 14.9% in 1versus 1.69 ms and 15.7% in 2. The emission peak shows significant redshift (79 nm) in 2 regarding 1, which arises from their distinction of coordination interactions between Pb2+ ion and FDA2− ligand in both CPs.