The self-assembly reactions of transition metal ions and 1,3,5-benzenetricarboxylic acid (H(3)btc) in the presence of auxiliary aromatic bidentate ligands 1,10-phenanthroline (1,10-phen) or 4,4-bipyridine-N,N-dioxide (4,4-bpdo) have isolated four coordination polymers [Co-18(btc)(10)(H2O)(6)(OH)(6)(1,10-phen)(6)]14H(2)O3DMF (1) and [M-3(btc)(2)(H2O)(4)(4,4-bpdo)]2H(2)O2DMF [M = Co (2), Mn (3), Ni (4)]. Single-crystal X-ray diffraction analysis revealed that the M-3 clusters in the structure of 1-4 are connected by hydroxyl group oxygen atoms (or oxygen atoms from 4,4-bpdo ligands) and carboxyl groups to generate a three-dimensional framework. The network of final assemblies can be adjusted by varying the type of auxiliary ligands (1,10-phen, 4,4-bpdo). In addition, the gas adsorption properties of 2 are also investigated.