Eight new compounds, namely, [Cu2(L)]·2NO3·H2O (1), [Cu(ox)2]·0.5(H6L)·3H2O (2), [Zn(L)0.5(nds)0.5] (3), [Zn4(L)2(m-bdc)2]·0.5H2O (4), [Cd(L)0.5(ox)0.5(H2O)]·MeOH·1.25H2O (5), [Cd(L)0.5(H2O)3]·0.5(p-bdc)·1.5H2O (6), [Cd2(L)(btec)0.5(H2O)4]·2.5MeOH·H2O (7) and [Ni2(L)(btec)0.5(H2O)]·MeOH·1.5H2O (8) (H2L=10,21-dimethyl-3,6,14,17-tetraazatricyclo [17.3.18,12]tetracosa-1(23),8,10,12(24),19,21-hexaene-23,24-diolate, ox=oxalate, nds=1,5-naphthalenedisulfonate, m-bdc=1,3-benzenedicarboxylate, p-bdc=1,4-benzenedicarboxylate and btec=1,2,4,5-benzenetetracarboxylate), have been synthesized. In compound 1, the L ligand coordinates with two Cu(II) atoms to form a [Cu2L]2+ unit. In compound 2, two ox anions chelate to one Cu(II) atom to form a [Cu(ox)2]2− unit. The (H6L)4+ acts as a counter ion. The whole structures of 1 and 2 feature three-dimensional (3D) supramolecular architectures connected by weak Cu⋯O and hydrogen-bonding interactions, respectively. In compounds 3–5, the [M2L]2+ cations are bridged by nds, m-bdc and ox anions to form chains, respectively. The chains of 3 and 4 are further linked by hydrogen-bonding interactions into 2D and 3D supramolecular architectures, respectively. In compound 6, the macrocyclic L anion coordinates to two Cd(II) atoms to form a [Cd2L]2+ cation. The final structure of 6 exhibits a 3D supramolecular architecture linked by hydrogen bonds. In compound 7, Cd(II) atoms are linked by L anions to form two types of [Cd2L]2+ cations. One type of [Cd2L]2+ cations are bridged by btec anions to generate a polymeric anion chain, whereas the other [Cd2L]2+ cations are free. Further, the polymeric anion chains and the [Cd2L]2+ cations are linked by hydrogen bonds to generate a 2D supramolecular layer. In compound 8, btec anion bridges the [Ni2L]2+ cations to yield a 2D layer. Thermogravimetric analyses (TGA) for the compounds 1–8 have been investigated. In addition, the magnetic property for 1 and the luminescent properties for compounds 3–7 have also been studied.