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Five new Cd(II) complexes, {[Cd1.5(tzia)(H2O)2]·H2O}n (1), {[Cd1.5(tzia)(H2O)4]·1.5H2O}n (2), [Cd(H2tzia)2(H2O)4]·H2O (3), [Cd5(μ3-OH)(tzia)3(H2O)7]·2H2O}n (4), and {[Cd2(μ3-OH)(tzia)(H2O)2]·H2O}n (5) (H3tzia = 5-(1H-tetrazol-5-yl)isophthalic acid), were assembled employing a tetrazolyl-carboxyl ligand H3tzia with Cd(II) ions, revealing versatile structures from zero-dimensional (0D) mononuclear molecule, 2D layer to 3D framework, in which five new types of coordination modes of H3tzia were observed. Complex 1 shows a 3D (3,6)-connected ant net based on trinuclear [Cd3(COO)2(N4C)2] cluster; 2 forms an unusual 3D (3,4)-connected 3,4T1 net with 1D tubes based on the 26-membered metallocycles; 3 is a mononuclear molecule; 4 displays an unprecedented (3,4,10)-connected 2D layer based on pentanuclear [Cd5(μ3-OH)(COO)2(N4C)3] cluster; 5 is a 3D porous framework containing 1D Cd-hydroxy-tetrazolyl ribbons. Complexes 1–5 exhibit strong luminescence with different energies resulted from the various coordination mo...