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The first series of mixed succinate/sulfate/Ln MOFs, [Ln 2 (C 2 H 4 C 2 O 4 ) 2 (SO 4 )(H 2 O) 2 ] (RPF-16), where Ln ¼ La, Pr, Nd, and Sm, were hydrothermally obtained and their structures determined by X-ray single crystal diffraction. The crystalline products are a series of isostructural 3D polymeric compounds that crystallise in the monoclinic space group P2(1)/n. Their framework comprises infinite crossing chains of LnO 9 sharing edges polyhedra, kept together by succinate and sulfate anions. Topological simplification gives rise to a 3D uninodal six connected net of type pcu alpha-Po primitive cubic. These well-defined compounds show high chemoselectivity towards reduction of the nitro group and present bifunctional activity for the one-pot reductive amination of heptanal at near-complete conversion of the substrates. A general overview of the room-temperature luminescence behavior in the new RPF-16 Ln materials is also reported.