Assembly of Framework-Isomeric 4d4f Heterometallic MetalOrganic Frameworks with Neutral/Anionic Micropores and Guest-Tuned Luminescence Properties

Framework-isomeric three-dimensional (3D) CdLn heterometallic metalorganic frameworks (HMOFs), {[Ln2(ODA)6Cd3(H2O)6]6H2O}n (Ln=Gd (1a) and Tb (1b), ODA=oxydiacetic acid) and {[Cd(H2O)6][Ln2(ODA)6Cd2]H2O}n (Ln=Gd (2a), Tb (2b)), with neutral and anionic pores, respectively, were designed based on a lanthanide metalloligand strategy and synthesized by using a stepwise assembly and a hydrothermal method. Luminescence studies revealed that 1b and 2b can act as luminescent metalorganic frameworks and their light-emitting properties can be modulated by small guest molecules and the manganese counterion, respectively.