Hydrothermal Synthesis, Structure Characterization And Properties Of Polyoxometalates Based On Tungstoborates

On the basis of molecular design and assembly, a series of polyoxometalates constructed from Keggin [BW12O40]5– polyanions as building blocks were successfully synthesized by hydrothermal technique, and characterized by X-ray crystallography, spectroscopic and thermal properties.I. We obtained two organic-inorganic composites based on Keggin Tungstoborates:1. [Mn(phen)3]2H[BW12O40]?3H2O: size 0.12×0.10×0.09 mm, Monoclinic system, C2/c space group, a = 27.285(3)?, b = 25.060(3)?, c = 16.336(18) ?,β= 104.911(2)°, V =10794(2)?3, Z = 4, R1 =0.0784, wR2 = 0.1999.2. [Cu(en)2(H2O)][Cu(en)2]2H3[BW11.75Cu0.25O40]·3.75H2O: size 0.12×0.10×0.09 mm, Orthorhombic system, Pbca space group, a = 21.5438(18)?, b = 20.6591(18)?, c = 26.052(2)?,β= 90.00°, V = 11595.2(17)?3, Z = 8, R1 = 0.0306, wR2 = 0.0666.II. The supported polyoxometalates based on Keggin polyanion:3. [Mn(2,2'-bipy)3]1.5[BW12O40Mn(2,2'-bipy)2(H2O)]?0.25H2O: size 0.12×0.10×0.08, Monoclinic system, C2/c space group, a = 46.812(16)?, b = 14.447(5)?, c = 26.083(9)?,β= 90°, V = 17639(11)?3, Z = 8, R1 = 0.0561, wR2 = 0.1451.4. [Fe(2,2'-bipy)3]1.5[BW12O40Fe(2,2'-bipy)2(H2O)]?0.5H2O: size 0.14×0.12×0.11, Monoclinic system, C2/c space group, a = 46.633(5)?, b = 14.3156(16)?, c = 25.976(3)?,β= 90°, V = 17341(3)?3, Z = 8, R1 = 0.0457, wR2 = 0.0771.5. [Cu2(phen)2(OH)2]2H[Cu(H2O)2{BW12O40Cu0.75(phen)(H2O)}2]?1.5H2O: size 0.15×0.13×0.11, Monoclinic system, C2/c space group, a = 43.888(9)?, b = 23.966(5)?, c = 13.744(3) ?,β= 102.77(3)°, V = 14099(5)?3, Z = 4, R1 = 0.0695, wR2 = 0.1111.6. [Co(2,2′-bipy)3]1.5[SiWVWVI11O40Co(2,2′-bipy)2(H2O)]·0.5H2O: size 0.12×0.10× 0.09, monoclinic system, C2/c space group, a = 46.995(15)A, b = 14.487(5)A, c = 26.205(9)A,β= 90.000(0)°, V = 17841(10)A3, Z = 4, R1 = 0.0660, wR2 = 0.0660.III. The rare earth derivative based on monovacant Keggin units:7. [Cu(en)2]2H8[Gd(PW11O39)2]A(H2en)0.5A3H2O: size 0.11×0.11×0.10, Triclinic system, P-1 space group, a = 12.651(2) A, b = 20.559(3) A, c = 21.729(3) A,α= 71.379(2),β= 82.829(2),γ= 75.532(2)°, V = 5179.5(14)A3, Z = 2, R1 = 0.0702, wR2 = 0.1479.IV. The supported polyoxometalate based onβ-octamolybdate anion:8. H4{[Cu2(ophen)2]2[Mo8O26]}[Cu2(ophen)2]·H2O: size 0.16×0.14×0.13, Triclinic system, P-1 space group, a = 9.9091(8) A, b = 13.3981(8) A, c = 14.8266(10) A,α= 84.6310(10),β= 83.0620(10)°,γ= 77.7800(10), V = 1905.0(2)A3, Z = 1, R1 = 0.0269, wR2 = 0.0669.