Three new cadmium or zinc arenedisulfonate complexes [Zn（bpp）2（L）]n 1, { [Cd（bpp）2（1,5-NDS）（H2O）2]·4H2O }n 2 and { [Cd（bpp）2（H2O2）2]·（1,5-NDS） } n 3 （L = 4,4′-bis（2-sulfonatostyryl）biphenyl, bpp = 1,3-di（4-pyd-dyl）propane and 1,5-NDS = 1,5-Naphthalenedisulfonate） have been synthesized from aqueous solution and structurally characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Crystal data for complex 1： space group P21/n, a = 10.559（3）, b = 13.138（4）, c = 17.623（5）A^°, β = 100.852（3）°, V = 2400.9（12） A^°^3 Z = 2, Dc= 1.351 g/cm^3, F（000） = 1016, μ = 0.654 mm^-1, the final R = 0.0412 and wR = 0.0994; Crystal data for complex 2： space group P^-1, a = 8.5642（19）, b = 10.076（3）, c = 12.114（3） A^°, α = 81.623（7）, β = 77.149（8）, γ = 82.787（7）°, V = 1003.6（4） A^°^3 Z = 1, Dc= 1.495 g/cm^3, F（000） = 466,μ = 0.713 mm^3, the final R = 0.0241 and wR = 0.0713; Crystal data for complex 3： space group C2/c, a = 21.6024（15）, b = 9.4608（5）, c = 18.4656（11）A^°, β = 107.359（3）°, V= 3602.0（4）A^°^3 Z = 4, Dc= 1.533 g/cm^3, F（000） = 1704,μ = 0.780 mm^-1, the final R = 0.0229 and wR = 0.0572. The X-ray single diffraction reveals that 1 exhibits a 3D metal-organic framework formed from 2D Zn（bpp）2^2＋ networks connected by L in the third dimension; 2 and 3 possess 3D and 2D architectures constructed from 1D polymeric chains through H-bond. Complexes 1-3 display photoluminescent emissions at 452 and 335 nm, respectively.
The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.
