Graphical abstract The self-assembly of CdII ions and 2,2′-dinitrobiphenyl-4,4′-dicarboxylate ligand leads to three CdII-based CPs, templated by different N-donor ligands, and exhibit diverse architectures, topologies, and highly selective luminescence sensing for Fe3+ ions. Highlights • Compound 1 exhibits 4-fold interpenetrated 3D dia net based on Cd 2 (OCO) 3 cluster. • Compound 3 exhibits 6-fold interpenetrated 3D dia net based on mononuclear CdII ions. • Compound 3 exhibits highly selective chemical sensing for Fe3+ ions in aqueous solution. Abstract Three CdII-based coordination polymers (CPs), formulated as [Cd 2 (dnpdc) 3 (DMSO) 3 ·0.5H 2 O] n (1), [Cd(dnpdc)(bpee)] n (2) and {Cd(dnpdc)(bimb)·2H 2 O} n (3) have been successfully synthesized and structurally characterized. Compound 1 exhibits a 4-fold interpenetrated 3D diamond network based on dinuclear Cd 2 (OCO) 3 cluster. Compound 2 features 3D frameworks constructed from the 2D [Cd(dnpdc)] n sheets pillared by 1D zig-zag shaped [Cd(bpee)] n chains. In compound 3 , the mononuclear CdII units are mixed connected by the dnpdc2− and bimb ligands, yielding the 6-fold interpenetrated 3D diamond network. The fluorescence measurements reveal that three compounds exhibit intense blue emission in the solid state. In particular, compound 3 exhibits highly selective chemical sensing for Fe3+ ions in aqueous solution. [ABSTRACT FROM AUTHOR]