Three new CdII coordination polymers (CPs) have been synthesized by hydrothermal reactions of Cd(OAc)2, 1,2,5‐thiadiazole‐3,4‐dicarboxylic acid (H2tdzdc), and distinct N/O‐donor ligands. They exhibit two‐dimensional (2D) and three‐dimensional (3D) structures with different topology networks including rob, zzx, and cem. The introduction of 4,4‐bipyridine (4,4‐bipy), [4,4‐bipyridine]1,1‐dioxide (Obpy), and 1,4‐bis((1H‐1,2,4‐triazol‐1‐yl)methyl)benzene (tmb) is a favor for the construction of interpenetrated networks. Moreover, the luminescent properties of 1, 2, and 3 have been investigated in detail by experiment and theoretical methods. Density functional theory (DFT) calculations indicate that the electron would be transferred from metal to ligand in the excitation of compound 3.
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