Photochemical Synthesis, Properties and X-Ray Crystal Structure of Tetrabutylammonium Dodecamolybdop

来源 :Chinese Journal of Chemistry | 被引量 : 0次 | 上传用户:m397760109
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The title heteropoly blue, (Bu 4N) 6H 10[PMo VI 11Mo VO 40] 4·H 2O has been photochemically synthesized and characterized with elemental analysis, solid diffusion reflectance electronic spectra, CV, ESR, XPS, IR spectra, conductivity measurement and X-ray single crystal analysis. The crystallographic data for C 96H 218Mo 48N 6O 169P 4 are as follows: M r=8889.76, triclinic, Pī, a=1.4142(3) nm, b=2.6027(5) nm, c=2.6403(5) nm, α=113.96(3)°, β=90.05(3)°, γ=105.71(3)°, V=8.481(3) nm 3, Z=1, D c=1.741 g/cm 3, F(000)=4264, μ=1.798 mm -1. The X-ray crystal structure analysis reveals that there is one independent molecule in the unit cell of the title heteropoly blue which contains four mixed-valence heteropoly anions, six tetrabutylammonium cations and one water molecule. Its molecular structure possesses a centrosymmetrical arrangement in the unit cell. The phosphorus atom is in the crystallographic inversion center of the heteropoly anion and the eight oxygen atoms surrounding central phosphorus atom comprise of a distorted hexahedron. Heteropoly anion has two equal sets of PO 4 tetrahedron. The PO 4 tetrahedron and the MoO 6 octahedron in the polyanion are greatly distorted. The title heteropoly blue, (Bu 4N) 6H 10 [PMo VI 11Mo VO 40] 4 · H 2O has been photochemically synthesized and characterized with elemental analysis, solid diffusion reflectance electronic spectra, CV, ESR, XPS, IR spectra, conductivity measurement and The crystallographic data for C 96H 218Mo 48N 6O 169P 4 are as follows: M r = 8889.76, triclinic, Pī, a = 1.4142 (3) nm, b = 2.6027 (5) nm, c = 2.6403 (5) nm, α = 113.96 (3) °, β = 90.05 (3) °, γ = 105.71 (3) °, V = 8.481 (3) nm 3, Z = 1, D c = 1.741 g / cm 3 , F (000) = 4264, μ = 1.798 mm -1. The X-ray crystal structure analysis reveals that there is one independent molecule in the unit cell of the title heteropoly blue which contains four mixed-valence heteropolyanions, six tetrabutylammonium cations and one water molecule. Its molecular structure possesses a centrosymmetrical arrangement in the unit cell. The phosphorus atom is in the crystallographic inversion center of the heteropoly anion and the eight oxygen atoms surrounding central phosphorus atom comprise of a distorted hexahedron. Heteropoly anion has two equal sets of PO 4 tetrahedron. The PO 4 tetrahedron and the MoO 6 octahedron in the polyanion are greatly distorted.
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