Abstract
Two 3d–4f heterometallic monovacant Keggin phosphotungstate derivatives [Cu(dap)(H2O)2]0.5[Cu(dap)2]4H2[Pr(α-PW11O39)2] · 3H2O (1) and [Cu(en)2(H2O)]2[Cu(en)2]1.5H4[Pr(α-PW11O39)2] · 10H2O (2) (dap = 1,2-diaminopropane, en = ethylenediamine) have been hydrothermally synthesized by reaction of the trivacant Keggin phosphotungstate precursor Na9[A-α-PW9O34] · 7H2O with CuCl2 · 2H2O and PrCl3 in the presence of dap or en and structurally characterized by elemental analyses, IR spectra, X-ray single-crystal diffraction, and thermogravimetric analyses. Compound 1 crystallizes in the triclinic space group P 1 with a = 17.325(3), b = 18.917(3), c = 19.938(3) Å, α = 104.481(2), β = 98.968(3), γ = 91.306(3)°, V = 6236.4(18) Å3, Z = 2, GOOF = 1.000, R 1 = 0.0806, wR 2 = 0.2016. Compound 2 also belongs to the triclinic space group P 1 with a = 16.005(4), b = 18.053(4), c = 21.127(5) Å, α = 113.894(3), β = 90.745(4), γ = 94.255(4)°, V = 5560(2) Å3, Z = 2, GOOF = 0.999, R 1 = 0.0686, wR 2 = 0.1885. Both 1 and 2 display organic–inorganic hybrid 2-D sheet architectures built by classic mono-PrIII sandwiched dimeric moieties [Pr(α-PW11O39)2]11− through [Cu(L)2]2+ bridges (L = dap, en), which represent rare organic–inorganic hybrid 2-D 3d–4f heterometallic monovacant Keggin polyoxometalates.
Acknowledgments
We are thankful for financial support from the Natural Science Foundation of China (nos 21071043, 21071042), China Postdoctoral Science Foundation funded project (20100470996), the Natural Science Foundation of Henan Province (nos 092300410119, 102300410093), the Natural Science Foundation of Henan University (no. 2008YBZR010), the Postdoctoral Science Foundation of Henan University (no. BH2010003), the Foundation of Education Department of Henan Province (nos 2009A150003, 2010B150006), and Students Innovative Pilot Plan of Henan University (no. 09NB005).