Syntheses and Properties of Two Complexes Based on Keggin-type Polyoxometalate

Two unusual complexes [Cd2(Do)4(H2 O)2 Cl](PW12 O40) 2H2 O(1) and [Ag4(Do)6(PW12 O40)][Ag(Do)2 ]2(PW12 O40) 2H2 O(2) were hydrothermally synthesized by the combination of two different metallic salts, Keggin-type polyoxometalate and 1,10-phen-5,6-dione(Do), and characterized by elemental analyses, inductively coupled plasma analyses, infrared spectra, X-ray photoelectron spectroscopy, thermal gravimetry, photoluminescent spectra and single-crystal X-ray diffraction analyses. Crystal 1 is of monoclinic, space group P21 /n with a = 12.383(3), b = 18.326(4), c = 16.437(3), β = 90.29(3)o, V = 3730.1(13) 3, Z = 2, Cd2 C48 H32 N8 ClO52 PW12, Mr = 4050.24, Dc = 3.604 g·cm-3, μ(MoKα) = 19.145 mm-1, F(000) = 3608, GOOF = 1.168, the final R = 0.0569 and wR = 0.0745 for 5715 observed reflections(I 2σ(I)). Crystal 2 is of triclinic, space group P1 with a = 13.959(5), b = 16.972(5), c = 17.647(5), α = 85.970(5), β = 81.353(5), γ = 86.316(5)o, V = 4117(2) 3, Z = 1, Ag6 C120 H64 N20 O102 P2 W24, Mr = 8539.47, Dc = 3.444 g·cm-3, μ(MoKα) = 17.511 mm-1, F(000) = 3828, GOOF = 1.033, the final R = 0.0981 and wR = 0.1658 for 9906 observed reflections(I 2σ(I)). Structural analyses show that complex 1 has a zero dimensional structure, which is further assembled into a one-dimensional ladder-like structure through hydrogen bonds. Complex 2 possesses a one-dimensional chain structure. Furthermore, solid-state luminescent spectra of complexes 1 and 2 indicate red and green fluorescent emission, respectively.