Hydro- and solvo-thermal reactions of d-block metal ions (Mn(2+), Co(2+), Zn(2+) and Cd(2+)) with monosodium 2-sulfoterephthalate (NaH(2)stp) form six 3D coordination polymers featuring cluster core [M(4)(μ(3)-OH)(2)](6+) in common: [M(2)(μ(3)-OH)(stp)(H(2)O)] (M = Co (1), Mn (2) and Zn (3)), [Zn(2)(μ(3)-OH)(stp)(H(2)O)(2)] (4), [Zn(4)(μ(3)-OH)(2)(stp)(2)(bpy)(2)(H(2)O)]·3.5H(2)O (5) and [Cd(2)(μ(3)-OH)(stp) (bpp)(2)]·H(2)O (6) (stp = 2-sulfoterephthalate, bpy = 4,4'-bipyridine and bpp = 1,3-di(4-pyridyl)propane). All these coordination polymers were characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric and elemental analysis. Complexes 1-3 are isostructural coordination polymers with 3D frameworks based on the chair-like [Zn(4)(μ(3)-OH)(2)](6+) core and the quintuple helixes. In complex 4, there exist double helixes in the 3D framework based on the chair-like cluster cores. Complex 5 possesses a 2-fold interpenetration structure constructed from boat-like cluster core and the bridging ligands stp and bpy. For complex 6, the chair-like cluster cores and stp ligands form a 2D (4,4) network which is further pillared by bpp linkers to a 3D architecture. Magnetic studies indicate that complex 1 exhibits magnetic ordering below 4.9 K with spin canting, and complex 2 shows weak antiferromagnetic coupling between the Mn(II) ions with g = 2.02, J(wb) = -2.88 cm(-1), J(bb) = -0.37 cm(-1). The fluorescence studies show that the emissions of complexes 3-6 are attributed to the ligand π-π* transition.