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Isomorphous Lanthanide Metal–Organic Frameworks Based on Biphenyldicarboxylate: Synthesis, Structure, and Photoluminescent Properties

We report the structures of six anionic, isomorphous metal–organic frameworks [Ln(bpdc)2–][NH2(CH3)2+], where Ln = La, Ce, Nd, Eu, Gd, Er, and bpdc2– = biphenyl-4,4′-dicarboxylate = –O2C(C6H4)2CO2–. The Ln(III) metal centers exhibit eight-coordinate binding to six different bpdc2– ligands (four of which are μ-2 bridging and two are bidentate) and the framework is charge-balanced by a dimethylammonium cation. The materials all possess the same 3D structure and crystallize in the orthorhombic space group Pbcn. All exhibit thermal stability up to ca. 300 °C and decompose to Ln2O3 after 800 °C. The Eu-based structure exhibits strong fluorescence in the 612–620 nm range. These materials significantly expand the known chemistry and luminescence of the less studied f-block metal–organic frameworks.